Solvent dispersion of composite resin and uses thereof

ABSTRACT

A solvent dispersion of a composite resin which comprises a solvent and a composite resin comprising a thermoplastic elastomer (A) and a polymer of copolymerizable monomers (B) comprising a monomer having an α,β-monoethylenically unsaturated group and other copolymerizable monomer(s), wherein the thermoplastic elastomer (A) is a propylene-based elastomer having a molecular weight distribution (Mw/Mn) of not more than 3 as measured by gel permeation chromatography (GPC), and the copolymerizable monomers (B) include at least one monomer containing no functional groups; and uses of the dispersion. The dispersion can be used to provide a coating material, primer, adhesive, additive, binder, film, and primer for strippable paints and traffic paints, which have excellent adhesiveness to various materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 10/556,504,filed Jun. 9, 2006, which was the National Stage filing under §371 ofPCT/JP2004/006316, filed Apr. 30, 2004, which in turn claims priority toJapanese Application No. 2003-133830, filed May 13, 2003, the entirecontent of each of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a solvent dispersion of a compositeresin, which comprises a solvent and a composite resin comprising athermoplastic elastomer (A) and a polymer of copolymerizable monomers(B) comprising a monomer having an α,β-monoethylenically unsaturatedgroup and other copolymerizable monomer(s), and uses thereof.

More specifically, the invention relates to a solvent dispersion of apolyolefinic composite resin, which is useful as a coating material anda primer for untreated polyolefin resin films, sheets, molded productsor the like, or as an adhesive, an additive, a binder, a film, a primerfor strippable paints and traffic paints, or the like, when formed intoa coating film.

BACKGROUND ART

Conventionally, polyolefinic resins have in general many advantages suchas good productivity, excellent moldability in accordance with variousmolding techniques, light weight, anti-rust property, impact resistanceand the like, and thus have been used in a wide range of applicationssuch as interior or exterior decorations for automobiles, ships or thelike, materials for domestic appliances, furniture, miscellaneous goodsand construction, and the like.

Since such molded products of polyolefinic resins are generallynon-polar as well as crystalline, unlike those polar synthetic resinsrepresented by polyurethane resins, polyamide resins, acrylic resins andpolyester resins, it is extremely difficult to perform coating oradhesion to these polyolefinic resins using a general-purpose resincomposition.

For this reason, when coating or adhesion is carried out onto apolyolefinic resin molded product, it has been traditional to enhanceadherence onto the product surface by treating the surface with a primeror by activating the surface. For example, in the case of an automobilebumper, desired coating or adhesion has been carried out after enhancingadhesiveness to the coating film by subjecting the bumper surface toetching with a halogen-based organic solvent such as trichloroethane, orafter subjecting the bumper to pretreatment such as corona dischargetreatment, plasma treatment and ozone treatment.

However, coating or adhesion using such conventionally knowngeneral-purpose resin compositions requires not only high facility costsbut also a long operation time. Also, the finishing cannot be doneuniformly and consistently, thus it being liable to cause variations inthe state of surface treatment.

Hence, in the past, for example, a composition comprising polyolefinincorporated with maleic acid (JP-B No. 62-21027, etc.), or acomposition comprising polyolefin modified by chlorination as the maincomponent (JP-B No. 50-10916, etc.) has been suggested as a coatingcomposition having an improvement in the above-described problems.However, although these compositions have excellent adhesiveness to thepolyolefinic molded product, etc., since they have poor weatherresistance, their use has been usually limited to the use as a primer orto the applications where weather resistance is not required. Therefore,in the case of performing coating with such compositions in applicationswhere weather resistance is required, typically two-coat finishinvolving complicated operations is needed.

For this reason, development of a coating material which allows one-coatfinish treatment, and which can exhibit excellent adhesiveness tomaterials even without any pretreatment and has excellent weatherresistance, is in progress, and in this pertinent art, there have beensuggested, for example, a resin which is obtained by copolymerization ofan acrylic monomer and a chlorinated polyolefin (JP-A No. 58-71966,etc.); a coating composition comprising a copolymer of ahydroxyl-containing acrylic monomer and a chlorinated polyolefin, and anisocyanate compound (JP-A No. 59-27968); and the like. However, sincethese materials contain chlorine, their effect on the environment hasbecome a matter of concern.

There have been also suggested a method of introducing unsaturated bondsto a polyolefin (JP-A No. 1-123812, JP-A No. 2-269109, etc.), a methodof introducing organic peroxide (JP-A No. 1-131220, etc.), a method ofusing bifunctional organic peroxide (JP-A No. 64-36614, etc.) and thelike, and these are the means to improve reactivity of polyolefin withradically polymerizable unsaturated monomers.

However, in many cases of the above-described resin compositions andmethods for preparation thereof, drawbacks are found such that reactionshould be carried out at dilute concentrations, particularly because ofthe viscosity problem; the efficiency of graft copolymerization topolyolefin is low; since there is a tendency that homopolymers ofradically polymerizable unsaturated monomers are generated, theresulting resin solutions are highly liable to undergo separation andcannot be used directly as such, in general; and the coating obtainedfrom these resin solutions has surface tackiness.

Moreover, with regard to adhesion between polyolefin and metal such asaluminum, resin dispersions of modified polypropylene (JP-A No.63-12651, etc.) have been suggested. However, since these dispersionsemploy raw materials having high melting points in order to reducetackiness of the coating film, they have a drawback that theheat-sealing temperature is high.

[Patent Document 1] JP-B No. 62-21027

[Patent Document 2] JP-B No. 50-10916

[Patent Document 3] JP-A No. 58-71966

[Patent Document 4] JP-A No. 59-27968

[Patent Document 5] JP-A No. 1-123812

[Patent Document 6] JP-A No. 2-269109

[Patent Document 7] JP-A No. 1-131220

[Patent Document 8] JP-A No. 64-36614

[Patent Document 9] JP-A No. 63-12651

The present invention is to provide a solvent dispersion of a compositeresin which solves the above-described problems of the prior arts.

That is, it is an object of the invention to provide a coating material,a primer, an adhesive, an additive, a binder, a film, and a primer forstrippable paints and traffic paints, which can be applied by spraycoating as the resin solution does not undergo separation; which show nofilm surface tackiness when applied to form a coating film; which resultin a coating film obtained by using a curing agent having an isocyanategroup in the molecule, which exhibits superior weather resistance ascompared with coating films of polyolefins modified by chlorination;which result in coating films that exhibit excellent adhesiveness tountreated polyolefinic resin films, sheets or molded products; and whichhave excellent heat-sealability at low temperatures.

SUMMARY OF THE INVENTION

The present inventors have devotedly conducted researches andinvestigations in order to achieve the above-described object, and as aresult, they found that a resin solution obtained from raw materialscomprising a specific thermoplastic elastomer (A) and copolymerizablemonomers (B) consisting of a monomer having an α,β-monoethylenicallyunsaturated group and other copolymerizable monomer(s), and a resinwhich is obtained from the resulting resin solution incorporated with acuring agent having an isocyanate group in the molecule, would be veryuseful in achieving the above-described object, thus completing theinvention.

Therefore, the present invention comprises the inventions as describedin the following [1] to [28]:

[1] A solvent dispersion of a composite resin, which comprises a solventand a composite resin comprising a thermoplastic elastomer (A) and apolymer of copolymerizable monomers (B) consisting of a monomer havingan α,β-monoethylenically unsaturated group and other copolymerizablemonomer(s), wherein the thermoplastic elastomer (A) is a propylene-basedelastomer having a molecular weight distribution (Mw/Mn) of not morethan 3 as measured by gel permeation chromatography (GPC), and thecopolymerizable monomers (B) include at least one monomer containing nofunctional groups;

[2] The solvent dispersion of a composite resin according to [1],wherein the solvent is an organic solvent and/or water;

[3] The solvent dispersion of a composite resin according to [1],wherein the solvent is water and contains basic substance(s);

[4] The solvent dispersion of a composite resin according to [1],wherein the solvent is water and contains surfactant(s);

[5] The solvent dispersion of a composite resin according to [1], whichis obtained by removing an organic solvent from a solvent dispersion ofa composite resin comprising the organic solvent and water as thesolvent, and which contains basic substance(s) or surfactant(s);

[6] The solvent dispersion of a composite resin according to any one of[3] to [5], which comprises water as the solvent, wherein thethermoplastic elastomer (A) and the copolymerizable monomers (B) arepresent in the same particle;

[7] The solvent dispersion of a composite resin according to [1],wherein the thermoplastic elastomer (A) has an intrinsic viscosity [η]of 0.1 to 12 dl/g as measured at 135° C. in decalin, and is apropylene-based elastomer (I) which contains (a) 50 to 93 mol % of aunit derived from propylene, (b) 5 to 50 mol % of a unit derived fromα-olefin, and (c) 2 to 40 mol % of a unit derived from ethylene, or apropylene-based elastomer (II) which contains (a) 50 to 95 mol % of aunit derived from propylene and (b) 5 to 50 mol % of a unit derived fromα-olefin;

[8] The solvent dispersion of a composite resin according to [1],wherein the thermoplastic elastomer is obtained by copolymerizingpropylene and α-olefin, or by copolymerizing propylene, α-olefin andethylene, in the presence of a catalyst for olefin polymerization whichcontains:

[i] a transition metal compound represented by the following formula(1):

wherein M is a transition metal atom from Groups IVb, Vb and VIb of thePeriodic Table of Elements; R¹, R², R³ and R⁴ are each a hydrogen atom,a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group or aphosphorus-containing group, and some of the adjacent groups may bebonded to each other and form a ring together with the carbon atom towhich these groups are attached; X¹ and X² may be identical with ordifferent from each other, and are each a hydrogen atom, a halogen atom,a hydrocarbon group having 1 to 20 carbon atoms, a halogenatedhydrocarbon group having 1 to 20 carbon atoms, a silicon-containinggroup, an oxygen-containing group or a sulfur-containing group; and Y isa divalent hydrocarbon group having 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group having 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, adivalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO₂—, —NR⁵—,—P(R⁵)—, —P(O)(R⁵)—, —BR⁵— or —AlR⁵—, wherein R⁵ is a hydrogen atom, ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms or ahalogenated hydrocarbon group having 1 to 20 carbon atoms, and

[ii] at least one compound selected from the group consisting of:

-   -   [ii-1] an organoaluminum compound,    -   [ii-2] an organoaluminum-oxy compound, and    -   [ii-3] a compound forming ion pairs by reacting with the        transition metal compound (1);

[9] The solvent dispersion of a composite resin according to [1],wherein the thermoplastic elastomer is obtained by copolymerizingpropylene and α-olefin, or by copolymerizing propylene, α-olefin andethylene, in the presence of a catalyst for olefin polymerization whichcontains:

[i] a transition metal compound represented by the following formula(2):

wherein M, R¹, R³, X¹, X² and Y have the same meanings as defined in theformula (1); and R²¹ to R²⁴ and R⁴¹ to R⁴⁴ are each a hydrogen atom, ahalogen atom, an alkyl group having 2 to 6 carbon atoms or an aryl grouphaving 6 to 16 carbon atoms, while this alkyl group or aryl group may besubstituted with halogen atom(s) or organic silyl group(s), and adjacentsubstituents may form a ring, and

[ii] at least one compound selected from the group consisting of:

-   -   [ii-1] an organoaluminum compound,    -   [ii-2] an organoaluminum-oxy compound, and    -   [ii-3] a compound forming ion pairs by reacting with the        transition metal compound (2);

[10] The solvent dispersion of a composite resin according to [1],wherein the thermoplastic elastomer is obtained by copolymerizingpropylene and α-olefin, or by copolymerizing propylene, α-olefin andethylene, in the presence of a catalyst for polymerization whichcontains:

[i] a transition metal compound represented by the following formula(3):

wherein M is a transition metal atom from Groups Mb, IVb, Vb, VIb, VIIband VIII of the Periodic Table of Elements;

m is an integer of 1 to 3;

Q is a nitrogen atom, or a carbon atom having a substituent R⁵²;

A is an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atomhaving a substituent R⁵⁶;

R⁵¹ to R⁵⁶ may be identical with or different from each other, and areeach a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group; and two or more ofthese may be joined together to form a ring; and when m is 2 or more,R⁵¹ groups, R⁵² groups, R⁵³ groups, R⁵⁴ groups, R⁵⁵ groups, and R⁵⁶groups may be identical with or different from each other and one of theR⁵¹ to R⁵⁶ groups in one ligand and one of the R⁵¹ to R⁵⁶ groups inanother ligand may be joined together;

n is a number satisfying the valence of M; and

X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group; and when n is 2 or more, X groups may be identicalwith or different from each other and may be bonded to each other toform a ring;

[11] The solvent dispersion of a composite resin according to [10],which is obtained by copolymerizing propylene and α-olefin, or bycopolymerizing propylene, α-olefin and ethylene, in the presence of acatalyst for olefin polymerization which further contains:

[iii] at least one compound selected from the group consisting of:

-   -   [iii-1] an organometallic compound,    -   [iii-2] an organoaluminum-oxy compound, and    -   [iii-3] a compound forming ion pairs by reacting with the        transition metal compound (3);

[12] The solvent dispersion of a composite resin according to any one of[8] to [11], wherein the α-olefin is 1-butene;

[13] The solvent dispersion of a composite resin according to [1], whichis formed by (1) polymerizing the thermoplastic elastomer (A) and thecopolymerizable monomers (B) in an organic solvent, (2) polymerizing thethermoplastic elastomer (A) and the copolymerizable monomers (B) andthen reacting the resulting polymer under radical generation in anorganic solvent, or (3) reacting the thermoplastic elastomer (A) and apolymer (C) composed of the copolymerizable monomers (B) under radicalgeneration in an organic solvent;

[14] The solvent dispersion of a composite resin according to [1],wherein the weight ratio of the thermoplastic elastomer (A) and thecopolymerizable monomers (B) is such that (A)/(B)=10/90 to 90/10;

[15] The solvent dispersion of a composite resin according to [1],wherein the thermoplastic elastomer (A) used is at least partly modifiedwith a functional group;

[16] A coating material containing the solvent dispersion of a compositeresin according to [1];

[17] A primer containing the solvent dispersion of a composite resinaccording to [1];

[18] An adhesive containing the solvent dispersion of a composite resinaccording to [1];

[19] An additive containing the solvent dispersion of a composite resinaccording to [1];

[20] A binder containing the solvent dispersion of a composite resinaccording to [1];

[21] A film which is obtained from the solvent dispersion of a compositeresin according to [1];

[22] A coating material which contains a main agent comprising thesolvent dispersion of a composite resin according to [1] having activehydrogen and/or a hydroxyl group, and a curing agent capable of reactingwith the active hydrogen and/or the hydroxyl group;

[23] A primer which contains a main agent comprising the solventdispersion of a composite resin according to [1] having active hydrogenand/or a hydroxyl group, and a curing agent capable of reacting with theactive hydrogen and/or the hydroxyl group;

[24] An adhesive which contains a main agent comprising the solventdispersion of a composite resin according to [1] having active hydrogenand/or a hydroxyl group, and a curing agent capable of reacting with theactive hydrogen and/or the hydroxyl group;

[25] An additive which contains a main agent comprising the solventdispersion of a composite resin according to [1] having active hydrogenand/or a hydroxyl group, and a curing agent capable of reacting with theactive hydrogen and/or the hydroxyl group;

[26] A binder which contains a main agent comprising the solventdispersion of a composite resin according to [1] having active hydrogenand/or a hydroxyl group, and a curing agent capable of reacting with theactive hydrogen and/or the hydroxyl group;

[27] A film which is formed by reacting a main agent comprising thesolvent dispersion of a composite resin according to [1] having activehydrogen and/or a hydroxyl group with a curing agent capable of reactingwith the active hydrogen and/or the hydroxyl group; and

[28] A coating film which is formed by applying the coating material,primer, adhesive, additive or binder according to [16] to [20], or acoating film which is formed by curing the coating material, primer,adhesive, additive or binder according to [22] to [26].

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Hereinafter, the present invention will be explained in detail.

The solvent dispersion of a composite resin of the invention can beprepared by performing polymerization while feeding copolymerizablemonomers (B) consisting of a monomer having an α,β-monoethylenicallyunsaturated group and other copolymerizable monomer(s), and apolymerization initiator to thermoplastic elastomer (A), or performingpolymerization while feeding a polymerization initiator to thermoplasticelastomer (A) and copolymerizable monomers (B) consisting of a monomerhaving an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s), and then reacting the product under radicalgeneration. Further, the solvent dispersion of a composite resin can bealso prepared by a method of reacting thermoplastic elastomer (A) and apolymer (C) which is composed of copolymerizable monomers (B) consistingof a monomer having an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s) under radical generation. Furthermore, thesolvent dispersion of a composite resin can be prepared by a method ofperforming polymerization while feeding copolymerizable monomers (B)consisting of a monomer having an α,β-monoethylenically unsaturatedgroup and other copolymerizable monomer(s), and a polymerizationinitiator to a thermoplastic elastomer (A) which is partly modified witha functional group, or performing polymerization while feeding apolymerization initiator to a thermoplastic elastomer (A) which ispartly modified with a functional group and copolymerizable monomers (B)consisting of a monomer having an α,β-monoethylenically unsaturatedgroup and other copolymerizable monomer(s), and then reacting theproduct to react. The solvent dispersion of a composite resin can bealso prepared by a method of reacting a thermoplastic elastomer (A)which is partly modified with a functional group, and a polymer (C)which is composed of copolymerizable monomers (B) consisting of amonomer having an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s) under radical generation.

The thermoplastic elastomer (A) used in the invention may be exemplifiedby propylene-based elastomer (I) or (II).

<Propylene-Based Elastomers (I) and (II)>

The propylene-based elastomers (I) and (II) used in the invention areprepared by copolymerizing propylene, 1-butene and ethylene, or bycopolymerizing propylene and 1-butene, in the presence of a catalyst forolefin polymerization which comprises [i] a specific transition metalcompound, and [ii] at least one compound selected from the groupconsisting of [ii-1] organoaluminum compounds, [ii-2] organoaluminum oxycompounds, and [ii-3] compounds forming ion pairs by the reaction withthe aforementioned transition metal compound (i). Transition metalcompound [i] is represented by the formula (1):

In the formula, M is a transition metal atom from Groups IVb, Vb and VIbof the Periodic Table of Elements, and it is specifically titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum ortungsten, preferably titanium, zirconium or hafnium, and particularlypreferably zirconium.

R¹, R², R³ and R⁴ may be identical with or different from each other andare each a hydrogen atom, a halogen atom, a hydrocarbon group having 1to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group or aphosphorus-containing group. Further, some of the adjacent groups may bebonded to each other and form a ring together with the carbon atom towhich the groups are bonded. Furthermore, R¹, R², R³ and R⁴, which areeach present in two, are such that when they are bonded to each other toform a ring, preferably the groups under the same symbol are combinedand bonded to each other. For example, it is preferable that R¹ and R¹are bonded to form a ring.

The halogen atom may be exemplified by fluorine, chlorine, bromine andiodine.

The hydrocarbon group having 1 to 20 carbon atoms may be exemplified byan alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl,2,3-dimethylbutyl, isopentyl, t-pentyl, neopentyl, cyclopentyl,isohexyl, n-hexyl, cyclohexyl, 4-methylcyclohexyl, octyl, nonyl,dodecyl, eicosyl, norbornyl and adamantyl; an alkenyl group such asvinyl, propenyl and cyclohexenyl; an arylalkyl group such as benzyl,phenylethyl, phenylpropyl and tolylethyl; an aryl group such as phenyl,tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl,biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl,benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl,tetrahydronaphthyl, indanyl and biphenylyl; and the like. Thehalogenated hydrocarbon group may be exemplified by the groups resultingfrom substitution of these hydrocarbon groups with halogen atoms.

Examples of the ring formed by bonding of these hydrocarbon groupsinclude a fused ring such as a benzene ring, a naphthalene ring, anacenaphthene ring and an indene ring, and a fused ring in which ahydrogen atom is substituted by a methyl group, an ethyl group, a propylgroup or a butyl group. The hydrocarbon groups may be substituted withhalogen atoms.

The silicon-containing group may be exemplified by a silicon-containingsubstituent including monohydrocarbon-substituted silyl such asmethylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such asdimethylsilyl and diphenylsilyl; trihydrocarbon-substituted silyl suchas trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl,triphenylsilyl, dimethylphenylsilyl, dimethyldiphenylsilyl,tritolylsilyl and trinaphthylsilyl; silyl ether ofhydrocarbon-substituted silyl such as trimethylsilyl ether;silicon-substituted alkyl such as trimethylsilylmethyl;silicon-substituted aryl such as trimethylphenyl; and the like.

The oxygen-containing group may be exemplified by a hydroxyl group; analkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxygroup such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; anarylalkoxy group such as phenylmethoxy and phenylethoxy; and the like.

The sulfur-containing group may be exemplified by sulfur-containinggroups in which oxygen of the above-mentioned oxygen-containingcompounds is substituted by sulfur; a sulfonate group such asmethylsulfonate, trifluoromethanesulfonate, phenylsulfonate,benzylsulfonate, p-toluenesulfonate, trimethylbenzylsulfonate,triisobutylbenzenesulfonate, p-chlorobenzenesulfonate andpentafluorobenzenesulfonate; and a sulfinate group such asmethylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate,trimethylbenzenesulfinate, pentafluorobenzenesulfinate andtrifluoromethanesulfinate.

The nitrogen-containing group may be exemplified by an amino group; analkylamino group such as methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino and dicyclohexylamino; an arylamino group oralkylaryl group such as phenylamino, diphenylamino, ditolylamino,dinaphthylamino and methylphenylamino; and the like.

The phosphorus-containing group may be exemplified by a phosphino groupsuch as dimethylphosphino and diphenylphosphino, and the like.

R¹ is preferably a hydrogen atom, a methyl group, a hydrocarbon grouphaving 2 to 6 carbon atoms, an aryl group or the like, and particularlypreferably a methyl group or a hydrocarbon group having 2 to 6 carbonatoms. R² and R⁴ are, among these, each preferably a hydrogen atom or ahydrocarbon group, and particularly preferably a hydrogen atom. R³ ispreferably a halogen atom or a hydrocarbon group which may besubstituted with a silicon-containing group, and inter alia, preferablya secondary or tertiary alkyl group having 3 to 20 carbon atoms, or anaryl group.

X¹ and X² may be identical with or different from each other, and areeach a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbonatoms, a silicon-containing group, an oxygen-containing group or asulfur-containing group.

For the specific atom or group, mention may be made of those describedfor R¹ to R⁴.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, adivalent halogenated hydrocarbon group having 1 to 20 carbon atoms, adivalent silicon-containing group, a divalent germanium-containinggroup, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO₂—,—NR⁵—, —P(R⁵)—, —P(O)(R⁵)—, —BR⁵— or —AlR⁵—, wherein R⁵ is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

The divalent hydrocarbon group may be exemplified by an alkylene groupsuch as methylene, dimethylmethylene, 1,2-ethylene,dimethyl-1,2-ethylene, 1,2-trimethylene, 1,4-tetramethylene,1,2-cyclohexylene, or 1,4-cyclohexylene; an arylalkylene group such asdiphenylmethylene or diphenyl-1,2-ethylene; or the like.

Also, the divalent halogenated hydrocarbon group having 1 to 20 carbonatoms may be exemplified by the halogenation products of theabove-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms,such as chloromethylene, or the like.

The divalent silicon-containing group may be exemplified by analkylsilylene, alkylarylsilylene or arylsilylene group such asmethylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene,di(isopropyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,diphenylsilylene, di(p-tolyl)silylene or di(p-chlorophenyl)silylene; analkyldisilyl, alkylaryldisilyl or aryldisilyl group such astetramethyl-1,2-disilyl or tetraphenyl-1,2-disilyl; or the like.

The substituent as the divalent germanium-containing group or divalenttin-containing group may be exemplified by the compounds in whichsilicon of the above-mentioned divalent silicon-containing groups issubstituted by germanium or tin, respectively.

Among these, preferred are the divalent silicon-containing groups, andparticularly preferred are alkylsilylene, alkylarylsilylene andarylsilylene.

In the followings, examples of the transition metal compound [i]represented by the formula (1) will be listed:bis(cyclopentadienyl)zirconium dichloride, bis(indenyl)zirconiumdichloride, bis(fluorenyl)zirconium dichloride,bis(n-propylcyclopentadienyl)zirconium dichloride,bis(t-butylcyclopentadienyl)zirconium dichloride,bis(trimethylsilylcyclopentadienyl)zirconium dichloride,bis(neopentylcyclopentadienyl)zirconium dichloride,rac-dimethylsilylenebis(1-cyclopentadienyl)zirconium dichloride,rac-dimethylsilylenebis{1-(3-methylcyclopentadienyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,4-dimethylcyclopentadienyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,3,5-trimethylcyclopentadienyl)}zirconiumdichloride and the like may be mentioned.

Among the transition metal compounds [i] represented by the formula (1),those represented by the formula (2) are preferred:

wherein M, R¹, R³, X¹, X² and Y have the same meaning as defined for theformula (1); R²¹ to R²⁴ and R⁴¹ to R⁴⁴ are each a hydrogen atom, ahalogen atom, an alkyl group having 2 to 6 carbon atoms or an aryl grouphaving 6 to 16 carbon atoms; this alkyl group or aryl group may besubstituted with halogen atom(s) or organic silyl group(s); and adjacentsubstituents may be bonded to each other to form a ring.

Specific examples thereof include rac-ethylenebis(1-indenyl)zirconiumdichloride, rac-ethylenebis(1-indenyl)zirconium dibromide,rac-ethylenebis(1-indenyl)dimethylzirconium,rac-ethylenebis(1-indenyl)diphenylzirconium,rac-ethylenebis(1-indenyl)methylzirconium monochloride,rac-ethylenebis(1-indenyl)zirconium bis(methanesulfonate),rac-ethylenebis(1-indenyl)zirconium bis(p-toluenesulfonate),rac-ethylenebis(1-indenyl)zirconium bis(trifluoromethanesulfonate),rac-ethylenebis{1-(4,5,6,7-tetrahydroindenyl)}zirconium dichloride andthe like; rac-dimethylsilylenebis(1-indenyl)zirconium dichloride,rac-dimethylsilylenebis{1-(2-methylindenyl)}zirconium dichloride,rac-dimethylsilylenebis{1-(2-methyl-4-isopropylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-ethylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-n-propylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-n-butylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-s-butylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-n-pentylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-n-hexylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-cyclohexylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-methylcyclohexylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-phenylethylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-phenyldichloromethylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-chloromethylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-trimethylsilylenemethylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-trimethylsiloxymethylindenyl)}zirconiumdichloride and the like;rac-diethylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-di(isopropyl)silylenebis{dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-di(n-butyl)silylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-di(cyclohexyl)silylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2,7-dimethyl-4-ethylindenyl)}zirconiumdichloride,rac-di(p-tolyl)silylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride,rac-di(p-chlorophenyl)silylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-methyl-4-isopropyl-7-ethylindenyl)}zirconiumdibromide,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdimethyl,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiummethyl chloride,rac-dimethylsilylenebis{1-(2,7-dimethyl-4-isopropyl-1-indenyl)}zirconium(trifluoromethanesulfonate),rac-dimethylsilylenebis{1-(2,7-dimethyl-4-isopropyl-1-indenyl)}zirconiumbis(p-phenylsulfinate) and the like;rac-dimethylsilylenebis{1-(2-phenyl-4-isopropyl-7-methyl-1-indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-α-acenaphthoindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4,5-benzoindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4,6-diisopropylindenyl)}zirconiumdichloride, rac-dimethylsilylenebis{1-(4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-methyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(1-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(2-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-methyl-4-(p-fluorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(pentafluorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(m-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(o-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(o,p-dichlorophenyl)phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-bromophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-tolyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(m-tolyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(o-tolyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(o,o′-dimethylphenyl)-1-indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-ethylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-isopropylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-benzylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-biphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(m-biphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(p-trimethylsilylenephenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-methyl-4-(m-trimethylsilylenephenyl)indenyl)}zirconiumdichloride, rac-dimethylsilylenebis{2-phenyl-4-phenylindenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdibromide,rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dimethyl,rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconium methylchloride, rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumchloride SO2Me,rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconium chlorideOSO2Me, rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride mono(trifluoromethanesulfonate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoromethanesulfonate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(p-toluenesulfonate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(methylsulfonate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoromethanesulfonate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoroacetate),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride (n-butoxide),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(n-butoxide),rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride (phenoxide) and the like;rac-methylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,rac-ethylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,rac-diisopropylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-di(n-butyl)silylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-dicyclohexylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-di(p-tolyl)silylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-di(p-chlorophenyl)silylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylgermylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylstannylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(o-methylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(m-methylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(p-methylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,5-dimethylphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,4,6-trimethylphenyl)indenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-ethyl-4-(o-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(m-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(p-chlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,3-dichlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2,6-dichlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(3,5-dichlorophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(2-bromophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(3-bromophenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(4-bromophenyl)indenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-ethyl-4-(4-biphenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-ethyl-4-(4-trimethylsilylenephenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-isopropyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isopropyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride and the like;rac-dimethylsilylenebis{1-(2-s-butyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(8-methyl-9-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-s-butyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-pentyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-pentyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-butyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-isobutyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-neopentyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-neopentyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-hexyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylsilylenebis{1-(2-n-hexyl-4-(α-naphthyl)indenyl)}zirconiumdichloride and the like;rac-methylphenylsilylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-methylphenylsilylenebis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-diphenylsilylenebis{1-(2-ethyl-4-(4-biphenyl)-indenyl)}zirconiumdichloride, rac-diphenylsilylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}and the like; rac-methylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride, rac-methylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride, rac-ethylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,rac-ethylenebis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylgermylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylgermylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylgermylenebis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylstannylenebis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,rac-dimethylstannylenebis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,rac-dimethylstannylenebis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,rac-dimethylstannylenebis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride and the like.

According to the invention, for the above-described compounds, atransition metal compound [i] in which zirconium is substituted bytitanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum ortungsten can be also used. The transition metal compound [i] is usuallyused as a component of a catalyst for olefin polymerization in the formof a racemate, and either (R) configuration or (S) configuration can bealso used. The transition metal compound [i] can be also used incombination.

According to the invention, for the compound [ii] which can activate thetransition metal compound [i] (hereinafter, also referred to as acomponent [ii]), at least one compound selected from [ii-1] anorganoaluminum compound, [ii-2] an organoaluminum oxy compound, and[ii-3] a compound forming ion pairs by the reaction with theabove-mentioned transition metal compound [i], is used.

The organoaluminum compound [ii-1] used in the invention is, forexample, represented by the following formula (4):

R¹ _(n)AlX_(3-n)  [Formula (4)]

wherein R¹ is a hydrocarbon group having 1 to 12 carbon atoms; X is ahalogen atom or a hydrogen atom; and n is from 1 to 3.

In the formula (4), R¹ is a hydrocarbon group having 1 to 12 carbonatoms, for example, an alkyl group, a cycloalkyl group or an aryl group,and specifically a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an isobutyl group, a pentyl group, a hexyl group, anoctyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, atolyl group or the like.

Specific examples of the organoaluminum compound [ii-1] include thefollowing compounds: trialkylaluminum such as trimethylaluminum,triethylaluminum, triisopropylaluminum, triisobutylaluminum,trioctylaluminum, tri(2-ethylhexyl)aluminum and tridecylaluminum;alkenylaluminum such as isoprenylaluminum; dialkylaluminum halide suchas dimethylaluminum chloride, diethylaluminum chloride,diisopropylaluminum chloride, diisobutylaluminum chloride anddimethylaluminum bromide; alkylaluminum sesquihalide such asmethylaluminum sesquichloride, ethylaluminum sesquichloride,isopropylaluminum sesquichloride, butylaluminum sesquichloride andethylaluminum sesquibromide; alkylaluminum dihalide such asmethylaluminum dichloride, ethylaluminum dichloride, isopropylaluminumdichloride and ethylaluminum dibromide; alkylaluminum hydride such asdiethylaluminum hydride and diisobutylaluminum hydride; and the like.

Further, for the organoaluminum compound [ii-1], a compound representedby the following formula (5) can be also used:

R¹ _(n)AlY_(3-n)  [Formula (5)]

wherein R¹ is the same as described above; Y is an —OR² group, an —OSiR³₃ group, an —OAlR⁴ ₂ group, an —NR⁵ ₂ group, an —SiR⁶ ₃ group or an—N(R⁷)AlR⁸ ₂ group; n is 1 or 2; R², R³, R⁴ and R⁸ are each a methylgroup, an ethyl group, an isopropyl group, an isobutyl group, acyclohexyl group, a phenyl group or the like; R⁵ is a hydrogen atom, amethyl group, an ethyl group, an isopropyl group, a phenyl group, atrimethylsilyl group or the like; and R⁶ and R⁷ are each a methyl group,an ethyl group or the like.

Specifically, the following compounds are listed.

(1) A compound represented by R¹ _(n)Al(OR²)_(3-n), for example,dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminummethoxide or the like;

(2) a compound represented by R¹ _(n)Al(OSiR²)_(3-n), for example,Et₂Al(OSiMe₃), (iso-Bu)₂Al(OSiMe₃), (iso-Bu)₂Al(OSiEt₃) or the like;

(3) a compound represented by R¹ _(n)Al(OAlR⁴ ₂)_(3-n), for example,Et₂AlOAlEt₂, (iso-Bu)₂AlOAl(iso-Bu)₂ or the like;

(4) a compound represented by R¹ _(n)Al(NR⁵ ₂)_(3-n), for example,Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN(SiMe₃)₂, (iso-Bu)₂AlN(SiMe₃)₂ orthe like;

(5) a compound represented by R¹ _(n)Al(SiR⁶ ₃)_(3-n), for example,(iso-Bu)₂AlSiMe₃ or the like; and

(6) a compound represented by R¹ _(n)Al(N(R⁷)AlR⁸ ₂)_(3-n), for example,Et₂AlN(Me)AlEt₂, (iso-Bu)₂AlN(Et)Al(iso-Bu)₂ or the like. These may beused individually or in combination.

Among these, the compounds represented by the formulas R¹ ₃Al, R¹_(n)Al(OR₂)₃, or R¹ _(n)Al(OAlR⁴ ₂)_(3-n) are preferred, and thecompounds wherein R¹ is an iso-alkyl group in the formulas arepreferred.

The organoaluminum compound [ii-2] used in the invention may beconventionally known, benzene-soluble aluminoxane, or thebenzene-insoluble organoaluminum oxy compounds as disclosed in JP-A No.2-78687.

Aluminoxane can be prepared by, for example, the following methods.

(1) A method of adding an organoaluminum compound such astrialkylaluminum, to a suspension of a compound containing adsorptionwater or of salts containing crystal water, for example, magnesiumchloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate,nickel sulfate hydrate, cerium(I) chloride hydrate or the like, in ahydrocarbon medium, and allowing to react;

(2) a method of subjecting an organoaluminum compound such astrialkylaluminum directly to the action of water, ice or steam, in amedium such as benzene, toluene, ethyl ether or tetrahydrofuran; and

(3) a method of reacting an organoaluminum compound such astrialkylaluminum with an organotin oxide such as dimethyltin oxide ordibutyltin oxide, in a medium such as decane, benzene or toluene.

Aluminoxane may also contain a small amount of organometalliccomponents. Further, from the above-described aluminoxane solutions thathave been recovered, the solvent or unreacted organoaluminum compoundsmay be removed by distillation and then redissolved in a solvent.

The organoaluminum compound used in preparation of aluminoxane may beexemplified by those listed as the organoaluminum compounds [ii-1].Specifically, trialkylaluminum and tricyclohexylaluminum areparticularly preferred. The organoaluminum compounds [ii-1] may be usedin combination of two or more species.

Examples of the solvent used in preparation of aluminoxanes includearomatic hydrocarbons such as benzene, toluene, xylene, cumene andcymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane,decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons suchas cyclopentane, cyclohexane, cyclooctane and methylcyclopentane;petroleum fractions such as gasoline, kerosene and diesel oil; orhalides, especially chloride, bromide and the like of theabove-mentioned aromatic hydrocarbons, aliphatic hydrocarbons andalicyclic hydrocarbons. In addition to these, ethers such as ethyl etherand tetrahydrofuran can be also used. Among these solvents, particularlyaromatic hydrocarbons are preferred.

Furthermore, the benzene-insoluble organoaluminum oxy compounds used inthe invention are such that the content of the Al component which issoluble in benzene at 60° C. is 10% or less, preferably 5% or less, andparticularly 2% or less, in terms of Al atoms, and the compounds areinsoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene (× %)is determined by measuring the amount of Al atoms (×millimoles) that arepresent in the entire filtrate obtained after the processes ofsuspending an amount of the organoaluminum oxy compound whichcorresponds to 100 milligram atoms of Al, in 100 ml of benzene, mixingthe suspension at 60° C. for 6 hours under stirring, subsequentlyperforming thermal time filtration the mixture at 60° C. using ajacketed G-5 glass filter, and washing the solid portion separated onthe filter with 50 cm³ of benzene for four times.

According to the invention, examples of the compound forming an ion pair[ii-3] by the reaction with the transition metal compound [i], which isused in formation of a catalyst for olefin polymerization, include theLewis acids, ionic compounds and carborane compounds described in JP-ANo. 1-501950, JP-A No. 1-502036, JP-A 3-179005, JP-A No. 3-179006, JP-ANo. 3-207703, JP-A No. 3-207704, U.S. Pat. No. 547,718 and the like.

Specifically, examples of the Lewis acid include triphenylboron,tris(4-fluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron,tris(3,5-dimethylphenyl)boron, tris(pentafluorophenyl)boron, MgCl₂,Al₂O₃, SiO₂—Al₂O₃ and the like.

Examples of the ionic compound include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate and the like.

Examples of the carborane compound include dodecaborane,1-carbaundecaborane, bis-n-butylammonium (1-carbadodeca)borate,tri-n-butylammonium (7,8-dicarbaundeca)borate, tri-n-butylammonium(tridecahydride-7-carbaundeca)borate and the like.

These may be used in combination of two or more species. According tothe invention, as the compound [ii] which can activate the transitionmetal compound [i], components [ii-1], [ii-2] and [ii-3] as describedabove can be used in combination.

The catalyst for olefin polymerization can be prepared by mixing theabove-described transition metal compounds [i] and component [ii] in aninert hydrocarbon solvent or an olefin solvent.

The inert hydrocarbon solvent used in preparation of the catalyst forolefin polymerization may be exemplified by aliphatic hydrocarbons suchas propane, butane, pentane, hexane, heptane, octane, decane, dodecaneand hexadecane; alicyclic hydrocarbons such as cyclopentane,cyclohexane, methylcyclopentane and cyclooctane; aromatic hydrocarbonssuch as benzene, toluene and xylene; halogenated hydrocarbons such asethylene chloride, chlorobenzene and dichloromethane; petroleumfractions such as gasoline, kerosene and diesel oil; and mixturesthereof.

In preparation of a catalyst from each of these components, thetransition metal compound [i] is preferably used in an amount of about10⁻⁵ to 10² mol/m³ (polymerization volume), and more preferably in anamount of about 10⁻⁴ to 5×10 mol/m³.

When the component [ii] that is to be used is the component [ii-1]and/or component [ii-2], the components are used in the amounts suchthat the atomic ratio of aluminum in component [ii] to the transitionmetal of the transition metal compound [i] (Al/transition metal) is from10 to 10,000, and preferably from 20 to 5,000. When these component[ii-1] and component [ii-2] are used together, they are used in theamounts such that the atomic ratio between the atomic ratio of aluminumin component [ii-1], [Al-1], and the atomic ratio between the atomicratio of aluminum in compound [ii-2], [Al-2], i.e., [Al-1]/[Al-2], ispreferably from 0.02 to 3, and more preferably from 0.05 to 1.5.

Furthermore, when the component [ii] that is to be used is the component[ii-3], it is used in an amount such that the molar ratio of transitionmetal compound [i] to component [ii-3] ([i]/[ii-3]) is preferably from0.01 to 10, and more preferably from 0.01 to 5.

The above-described components may be contacted in the polymerizationvessel, or alternatively preliminarily contacted and mixed, and thenadded to the polymerization vessel. In the case of preliminarilycontacting, the components can be contacted at a temperature of usually−50 to 150° C., and preferably −20 to 120° C., for 1 minute to 50 hours,and preferably 5 minutes to 25 hours. Also, upon contacting, the mixingtemperature may be changed.

The catalyst for olefin polymerization used in the invention may be asolid catalyst for olefin polymerization in which at least one of theabove-mentioned components [i] and [ii] is supported on a solid in thegranular or microparticulate form (support).

The support may be an inorganic support or an organic support. As theinorganic support, porous oxide is preferably used, and for example,SiO₂, Al₂O₃ or the like may be used. As the organic support, a polymeror copolymer containing, for example, an α-olefin having 2 to 14 carbonatoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene, orstyrene or vinyl cyclohexane as the main component, can be used.

The catalyst for olefin polymerization used in the invention can be alsoused in the form of prepolymerized catalyst that is prepared byprepolymerizing olefin with each of the above-described catalystcomponents. Examples of the olefin used in the prepolymerization includeolefins such as propylene, ethylene or 1-butene, and these may be alsoused in combination with other olefins.

According to the invention, in the preparation of a catalyst for olefinpolymerization, besides each of the components as described above, othercomponents that are useful in olefin polymerization, for example, wateras a catalyst component, can be also contained.

In addition, the propylene-based elastomers (I) and (II) that are usedin the invention can be prepared by copolymerizing propylene, 1-buteneand ethylene, or copolymerizing propylene and 1-butene, in the presenceof a catalyst for olefin polymerization comprising the transition metalcompound represented by the following formula (3):

wherein M is a transition metal atom from Groups Mb, IVb, Vb, VIb, VIIband VIII of the Periodic Table of Elements;

m is an integer of 1 to 3;

Q is a nitrogen atom or a carbon atom having a substituent R⁵²;

A is an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atomhaving a substituent R⁵⁶;

R⁵¹ to R⁵⁶ may be identical with or different from each other, and areeach a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group; two or more ofthese may be attached to each other to form a ring; when m is 2 or more,the R⁵¹ groups, R⁵² groups, R⁵³ groups, R⁵⁴ groups, R⁵⁵ groups and R⁵⁶groups may be respectively identical with or different from each other;and one group among R⁵¹ to R⁵⁶ contained in any one ligand may beattached to one group among R⁵¹ to R⁵⁶ contained in another ligand;

n is a number balancing the valence of M;

X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group; when n is 2 or more, X groups may be identicalwith or different from each other; or X groups may be bonded to eachother to form a ring.

Further, the propylene-based elastomers (I) and (II) used in theinvention can be also prepared by copolymerizing propylene, 1-butene andethylene, or copolymerizing propylene and 1-butene, in the presence of acatalyst for olefin polymerization comprising:

[i] a transition metal compound represented by the above-describedformula (3), and

[iii] at least one compound selected from the group consisting of

-   -   [iii-1] an organic metal compound,    -   [iii-2] an organoaluminum oxy compound, and    -   [iii-3] a compound forming ion pairs by the reaction with the        transition metal compound (3).

The propylene-based elastomers (I) and (II) of the invention can beprepared by copolymerizing propylene, 1-butene and ethylene, orcopolymerizing propylene and 1-butene, such that the consequentlytargeted composition ratio is achieved, in the presence of a catalystfor olefin polymerization as described above.

Polymerization can be carried out according to any of the liquid phasepolymerization methods such as suspension polymerization, solutionpolymerization, or the gas phase polymerization method. In a liquidphase polymerization method, the inert hydrocarbon solvent as used inthe preparation of the above-described catalyst can be used, orpropylene can be used as the solvent.

When polymerization is carried out by suspension polymerization, it iscarried out at a temperature of −50 to 100° C., and preferably 0 to 90°C. When polymerization is carried out by solution polymerization, it iscarried out at a temperature of 0 to 250° C., and preferably 20 to 200°C. When polymerization is carried out by gas phase polymerization, it iscarried out at a temperature of 0 to 120° C., and preferably 20 to 100°C., at a pressure of ambient pressure to 9.80 MPa, and preferablyambient pressure to 4.9 MPa.

Polymerization can be carried out in any of the batch mode, thesemi-continuous mode and the continuous mode. Furthermore, it can becarried out in two or more stages under different polymerizationconditions. The molecular weight of the resulting propylene-basedelastomer can be adjusted by allowing the presence of hydrogen in thepolymerization system, or by changing the polymerization temperature orpolymerization pressure.

With respect to the propylene-based elastomers (I) and (II) obtained bythe above-described methods, those having the following properties canbe suitably used.

<Propylene-Based Elastomer (I)>

{circle around (1)} Composition: The polymer contains (a) a unit derivedfrom propylene at a proportion of 50 to 93 mol %, preferably 60 to 90mol %, and more preferably 70 to 90 mol %; (b) a unit derived from1-butene at a proportion of 5 to 50 mol %, preferably 7 to 40 mol %, andmore preferably 10 to 35 mol %; and (c) a unit derived from ethylene ata proportion of 2 to 40 mol %, preferably 5 to 35 mol %, and morepreferably 7 to 30 mol %, wherein the proportion of the unit derivedfrom 1-butene is greater than the proportion of the unit derived fromethylene. The propylene-based elastomer (I) may further contain, inaddition to the above-mentioned three components, a unit derived fromdifferent kinds of olefin at a proportion of 10 mol % or less, forexample.

{circle around (2)} Intrinsic viscosity [η]: The intrinsic viscosity [η]as measured at 135° C. in decalin is 0.1 to 12 dl/g, preferably 0.3 to10 dl/g, and more preferably 0.5 to 8 dl/g.

{circle around (3)} Molecular weight distribution (Mw/Mn): The molecularweight distribution (Mw/Mn) determined by gel permeation chromatography(GPC) is 3 or less, preferably 1.5 to 3.0, and more preferably 1.5 to2.5.

{circle around (4)} Melting point (Tm): The melting point (Tm)determined by differential scanning calorimetry is preferably 100° C. orlower, and more preferably 90° C. or lower. A polymer whose meltingpoint is undetectable may be also used.

<Propylene-Based Elastomer (II)>

{circle around (1)} Composition: The polymer contains (a) a unit derivedfrom propylene at a proportion of 50 to 95 mol %, preferably 60 to 93mol %, and more preferably 70 to 90 mol %; and (b) a unit derived from1-butene at a proportion of 5 to 50 mol %, preferably 7 to 40 mol %, andmore preferably 10 to 30 mol %. The propylene-based elastomer (II) mayfurther contain, in addition to the above-mentioned two components, aunit derived from an olefin of different species at a proportion of 10mol % or less, for example.

{circle around (2)} Intrinsic viscosity [η]: The intrinsic viscosity [η]as measured at 135° C. in decalin is 0.1 to 12 dl/g, and preferably 0.3to 10 dl/g.

{circle around (3)} Molecular weight distribution (Mw/Mn): The molecularweight distribution (Mw/Mn) determined by gel permeation chromatography(GPC) is 3 or less, preferably 1.5 to 3.0, and more preferably 1.5 to2.5.

{circle around (4)}Melting point (Tm): The melting point (Tm) determinedby differential scanning calorimetry is preferably 140° C. or lower, andmore preferably 130° C. or lower. A polymer whose melting point isundetectable may be also used.

The thermoplastic elastomer (A) which is partly modified with functionalgroups, as described in the invention, can be obtained by reacting theabove-described propylene-based elastomer (I), (II) or a mixture ofthese two, with copolymerizable monomers consisting of a monomer havingan α,β-monoethylenically unsaturated group and other copolymerizablemonomer(s), which contain a below-described functional group. However,it is also allowable to use unreactive monomers in some portion.

As the copolymerizable monomers consisting of a monomer having anα,β-monoethylenically unsaturated group and other copolymerizablemonomer(s), which contain a functional group, as used herein, mentionmay be made of hydroxyl-containing vinyls such as hydroxyethyl acrylate,2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,lactone-modified hydroxyethyl (meth)acrylate and2-hydroxy-3-phenoxypropyl acrylate; carboxyl-containing vinyls such asacrylic acid, methacrylic acid, maleic acid, itaconic acid,ω-carboxy-polycaprolactone monoacrylate and phthalic acidmonohydroxyethyl acrylate; nitrogen compounds such as acrylamide,methacrylamide, methylolacrylamide and methylolmethacrylamide; andanhydrous carboxylic acids such as anhydrous maleic acid and anhydrouscitraconic acid. These may be used individually or in combination of twoor more species. The amount of addition of the above-describedcopolymerizable monomers consisting of a monomer having anα,β-monoethylenically unsaturated group and other copolymerizablemonomer(s), which contain a functional group, is in the range of 0.5 to20% by weight, and preferably 1 to 15% by weight, relative to the weightof the thermoplastic elastomer.

Examples of the copolymerizable monomers (B) consisting of a monomerhaving an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s), as used in the invention, include thefollowing.

As the monomer having an α,β-monoethylenically unsaturated group,mention may be made of (meth)acrylic acid esters such as methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl(meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate,2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, tridecyl(meth)acrylate, lauroyl (meth)acrylate, cyclohexyl (meth)acrylate,benzyl (meth)acrylate, phenyl (meth)acrylate, dimethylaminoethyl(meth)acrylate and diethylaminoethyl (meth)acrylate; hydroxyl-containingvinyls such as hydroxyethyl acrylate, 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, lactone-modified hydroxyethyl(meth)acrylate and 2-hydroxy-3-phenoxypropyl acrylate;carboxyl-containing vinyls such as acrylic acid, methacrylic acid,maleic acid, itaconic acid, ω-carboxy-polycaprolactone monoacrylate andphthalic acid monohydroxyethyl acrylate, and monoesterification productsthereof; epoxy-containing vinyls such as glycidyl (meth)acrylate andmethylglycidyl (meth)acrylate; isocyanate-containing vinyls such asvinyl isocyanate and isopropenyl isocyanate; aromatic vinyls such asstyrene, α-methylstyrene, vinyltoluene and t-butylstyrene; and inaddition, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpropionate, acrylamide, methacrylamide, methylolacrylamide andmethylolmethacrylamide, ethylene, propylene, C₄₋₂₀ α-olefins, and thelike. Macromonomers which have the above-mentioned monomers orcopolymers thereof as segments and have vinyl groups at the terminals,can be also used.

As the copolymerizable monomers comprising other copolymerizablemonomer(s) as used in the invention, mention may be made of anhydrouscarboxylic acids such as anhydrous maleic acid and anhydrous citraconicacid, and the like.

As the monomers in which copolymerizable monomers (B) have no functionalgroup, mention may be made of those obtained by excluding theabove-described copolymerizable monomers (B) consisting of a monomerhaving an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s), which contain a functional group, from theabove-described copolymerizable monomers (B) consisting of a monomerhaving an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s).

The expression “methyl (meth)acrylate” as described herein indicatesmethyl acrylate and methyl methacrylate.

These monomers preferably employ a monomer having anα,β-monoethylenically unsaturated group as the main component. Also,they may also employ a monomer having an α,β-monoethylenicallyunsaturated group as the main component, together with othercopolymerizable monomer(s) in combination.

The polymer (C) as used in the invention is composed of thecopolymerizable monomers (B) consisting of a monomer having anα,β-monoethylenically unsaturated group and other copolymerizablemonomer(s).

The ratio by weight of the thermoplastic elastomer (A), and thecopolymerizable monomers (B) consisting of a monomer having anα,β-monoethylenically unsaturated group and other copolymerizablemonomer(s) or their polymer (C) of the invention is such that(A)/(B)=10/90 to 90/10, or (A)/(C)=10/90 to 90/10, and preferably(A)/(B)=10/90 to 80/20, or (A)/(C)=10/90 to 80/20.

According to the invention, organic solvents including aromatichydrocarbons such as xylene, toluene and ethylbenzene; aliphatichydrocarbons such as hexane, heptane, octane and decane; alicyclichydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane;ester solvents such as ethyl acetate, n-butyl acetate, cellosolveacetate, propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate and 3-methoxybutyl acetate; ketone solvents suchas methyl ethyl ketone and methyl isobutyl ketone; and the like can beused, and mixtures of two or more of these can be also used. Among them,aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbonsare preferred, and aliphatic hydrocarbons and alicyclic hydrocarbons canbe suitably used. The amount of the organic solvent that can be used issuch that the proportion of non-volatile components of thermoplasticelastomer (A) when dissolved in the organic solvent is in the range of 5to 60% by weight.

The polymerization initiator that is used in the invention may beexemplified by organic peroxide such as di-tert-butyl peroxide,tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide,lauroyl peroxide, tert-butylperoxybenzoate and cumene hydroperoxide; andan azo compound such as azobis(isobutyronitrile),4,4′-azobis(4-cyanopentanoic acid) and2,2′-azobis(2-methyl-N-(2-hydroxyethyl)propionamide). These may be usedindividually or in combination of two or more species.

For the method of radical generation in the case where reaction isconducted by additionally generating radicals, conventionally knownmethods, for example, a method of irradiating light in the presence of aphotopolymerization initiator, a method of adding organic peroxide, orthe like, can be used.

Examples of the photopolymerization initiator include carbonyls such asbenzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin,ω-bromoacetophenone, chloroacetone, acetophenone,2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone,2-hydroxy-2-methylpropiophenone, 2-chlorobenzophenone,p-dimethylaminopropiophenone, p-dimethylaminoacetophenone,p,p′-bisdiethylaminobenzophenone, 3,3′,4,4′-tetrabenzophenone, Michler'sketone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutylether, benzoin n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphineoxide, benzyldimethyl ketal and methylbenzoyl formate; sulfides such asdiphenyl disulfide, dibenzyl disulfide and tetramethylthiurammonosulfide; quinones such as benzoquinone, anthraquinone,chloroanthraquinone, ethylanthraquinone and butylanthraquinone;thioxantones such as thioxantone, 2-methylthioxantone and2-chlorothioxantone; and the like. These may be used individually or incombination of two or more species. Further, these photopolymerizationinitiators may be used together with amines such as triethylamine,trimethylamine, triethanolamine, dimethylaminoethanol, pyridine,quinoline and trimethylbenzylammonium chloride; arylphosphines such astriphenylphosphine; thiol ethers such as β-thiodiglycol; and the like.

The above-mentioned photopolymerization initiator exhibits a significantstabilizing effect when used in an amount in the range of preferably0.01 to 10% by weight, and more preferably 0.1 to 5% by weight, relativeto the total weight of the above-mentioned thermoplastic elastomer (A)and copolymerizable monomers (B) or polymer (C).

Examples of the organic peroxide include di-tert-butyl peroxide,tert-butylperoxy-2-ethyl hexanoate, benzoyl peroxide, dicumyl peroxide,tert-butylperoxybenzoate, lauroyl peroxide, cumene hydroperoxide and thelike, each of which has a tert-butyl group and/or a benzyl group in themolecule. These may be used individually or in combination of two ormore species.

According to the invention, among the above-described organic peroxides,di-tert-butyl peroxide or tert-butylperoxy-2-ethyl hexanoate is morepreferably used. That is, organic peroxide having a tert-butyl groupand/or a benzyl group in the molecule has a relatively highhydrogen-withdrawing ability and an effect of improving the rate ofgrafting to polyolefin.

The above-described organic peroxide has a significant stabilizingeffect when used in an amount in the range of preferably 2 to 50% byweight, and more preferably 3 to 30% by weight, relative to the totalweight of thermoplastic elastomer (A) and copolymerizable monomers (B)or polymer (C). Also, this organic peroxide is preferably added in smallamounts, taking time as much as possible. That is, although it dependson the amount thereof to be used, the substance is preferably added insmall amounts over a long time, or in small amounts in many times.

In preparation of the above-described resins, at least one selected fromthe group consisting of fats and oils, derivatives of fats and oils,epoxy resins and polyester resins, can be used as a third component.

Examples of the fats and oils that are used as the third componentinclude linseed oil, soybean oil, castor oil, and purified productsthereof.

Examples of the derivatives of fats and oils that are used as the thirdcomponent include short oil alkyd resins, medium oil alkyd resins, longoil alkyd resins and the like, which have polybasic acid such asanhydrous phthalic acid and polyhydric alcohol such as pentaerythritoland ethylene glycol as the skeleton, and are modified with fats and oils(fatty acids); and further rosin-modified alkyd resins, phenol-modifiedalkyd resins, epoxy-modified alkyd resins, acrylated alkyd resins,urethane-modified alkyd resins and the like, which are modified withnatural resins, synthetic resins and polymerizable monomers.

Examples of the epoxy resin used as the third component include epoxyresins resulting from glycidyl etherification of bisphenol A, bisphenolF, novolac and the like; epoxy resins resulting from glycidyletherification of bisphenol A by adding propylene oxide or ethyleneoxide thereto; and the like. Amine-modified epoxy resins resulting fromaddition of multifunctional amine to the epoxy group may be also used.Furthermore, aliphatic epoxy resins, alicyclic epoxy resins, polyetherepoxy resins and the like may be mentioned.

The polyester resins that are used as the third component are thepolycondensation products of carboxylic acid components and alcoholcomponents. Examples of the carboxylic acid component include polybasiccarboxylic acids such as terephthalic acid, isophthalic acid, anhydrousphthalic acid, naphthalene dicarboxylic acid, succinic acid, glutaricacid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid,cyclohexanedicarboxylic acid, trimellitic acid, maleic acid and fumaricacid, and their esters with lower alcohols; hydroxycarboxylic acids suchas paraoxybenzoic acid; monobasic carboxylic acids such as benzoic acid;and the like. It is also possible to use them in combination of two ormore species.

Examples of the alcohol component include ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 3-methylpentanediol,2,2′-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol,trimethylolethane, trimethylolpropane, glycerin, pentaerythritol,ethylene oxide adduct of bisphenol A, a propylene oxide adduct ofbisphenol A, an ethylene oxide adduct of hydrogenated bisphenol A, apropylene oxide adduct of hydrogenated bisphenol A and the like, and twoor more species can be used in combination.

Also, it is possible to use a resin containing polymerizable unsaturatedbonds in the molecule, which is obtained by addition of anhydrouscarboxylic acid having polymerizable unsaturated bonds in the moleculeto the aforementioned polyester resins having a hydroxyl group.

The above-mentioned third component may be used alone or in acombination of two or more species. The component can be added to thereactor by feeding, or introduced into the reactor at the beginning andused. The amount of the third component to be added is usually 0.5 to60% by weight, and preferably 2 to 40% by weight, relative to the resincomponent.

In particular, the solvent dispersions of a composite resin prepared byusing fats and oils as well as derivatives of fats and oils as the thirdcomponent, have particularly good stability and good compatibility withother resins, as well as remarkably enhanced peel strength. Especially,a solvent dispersion containing castor oil has high effect.

According to the invention, mention may be made of a solvent dispersionof a composite resin containing water in the solvent, and its method forpreparation can be exemplified by the below-described methods.

The solvent dispersion of a composite resin can be prepared from theresin or resin liquid obtained by the above-described methods, by meansof a method of mixing the resin or resin liquid with ion-exchanged waterand a surfactant all at once and emulsifying the mixture, or optionallyremoving all or part of the organic solvent thereafter; or a method ofreplacing all or part of the solvent used in dissolution, dilution orsynthesis with a hydrophilic organic solvent, performing neutralizationby adding a basic substance, and then adding ion-exchanged water, oroptionally removing all or part of the organic solvent thereafter.

The surfactant used in the invention may be exemplified by a compoundhaving both a hydrophobic group and a hydrophilic group in the samemolecule, and examples thereof include an anionic surfactant, a nonionicsurfactant, a cationic surfactant, other reactive surfactants and thelike. These can be used individually or in combination of two or morespecies.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether,polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan ester,polyoxyethylene alkylamine ether and the like.

Examples of the anionic surfactant include fatty acid salts, higheralcohol sulfate esters, sodium alkylbenzenesulfonate, potassium oleate,a naphthalenesulfonic acid-formalin condensate, polyoxyethylene alkylether sulfate and the like. Particularly preferred are sodiumalkylbenzenesulfonate and potassium oleate.

Examples of the cationic surfactant include lauryltrimethylammoniumchloride, stearyltrimethylammonium chloride and the like.

The amount of the surfactant to be used is preferably about 0.05 to 40%by weight, more preferably about 0.1 to 20% by weight, and particularlypreferably about 0.1 to 10% by weight, relative to the resin comprisinga thermoplastic elastomer and copolymerizable monomers (B) consisting ofa monomer having an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s).

Further, examples of the hydrophilic organic solvent used in theinvention include alcohols such as methyl alcohol, ethyl alcohol,isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol,benzyl alcohol and cyclohexanol; ketones such as acetone, methyl ethylketone and methyl isobutyl ketone; ethers such as methyl cellosolve,ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol andbutyl carbitol; and the like. These may be used individually or incombination of two or more species. The content of the hydrophilicorganic solvent is preferably 50% or more, and more preferably 70% ormore, relative to the total solvent amount of the resin solution.

Examples of the basic substance include amines such as ethylamine,propylamine, butylamine, benzylamine, triethylamine, monoethanolamine,diethylamine, diethanolamine, trimethylamine, triethylamine,triisopropylamine, dimethylethanolamine, triethanolamine,methyldiethanolamine, diethylenetriamine and ethylaminoethylamine;ammonia; and hydroxides of alkaline earth metals and of alkali metalssuch as sodium hydroxide and calcium hydroxide. The amount of additionthereof for neutralization is 50 to 100 mol % of the carboxyl group.Also, they may be used in combination of two or more species.

In addition to the above, it is also possible to prepare the solventdispersion by polymerizing the copolymerizable monomers (B) consistingof a monomer having an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s), in the presence of an emulsion in which theparticles of the thermoplastic elastomer (A) are dispersed in water.

The emulsion having the thermoplastic elastomer (A) dispersed in wateris an emulsion in which the thermoplastic elastomer (A) is dispersed inwater by means of an emulsifier or a dispersant, and the methods forpreparation thereof are disclosed in JP-B No. 7-008933, JP-B No.5-039975 and the like.

For the initiator used in polymerization of the copolymerizable monomers(B) consisting of a monomer having an α,β-monoethylenically unsaturatedgroup and other copolymerizable monomer(s), any of those generally usedin emulsion polymerization can be used. Representative examples thereofinclude hydrogen peroxide; persulfates such as ammonium persulfate,potassium persulfate and sodium persulfate; organic peroxides such ascumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide,t-butylperoxy-2-ethylhexanoate and t-butylperoxybenzoate; azo compoundssuch as azobisisobutyronitrile; and redox initiators formed by theabove-mentioned ones combined with a reducing agent, including metalions such as iron ions, sodium sulfoxylate, formaldehyde, sodiumpyrosulfite, sodium hydrogen sulfite, L-ascorbic acid and Rongalite; andthe like. These may be used individually or in combination of two ormore species. Preferably used initiators are those having a solubilityin water of 10% or less, more preferably 5% or less, and most preferably1% or less.

Furthermore, it is also possible to use, if necessary, mercaptans suchas t-dodecylmercaptan and n-dodecylmercaptan; allyl compounds such asallylsulfonic acid, methallylsulfonic acid, and sodium salts thereof;and the like, as a molecular weight adjusting agent.

In addition, upon polymerization of the copolymerizable monomers (B)consisting of a monomer having an α,β-monoethylenically unsaturatedgroup and other copolymerizable monomer(s) in the presence of anemulsion of the thermoplastic elastomer (A), it is possible to use asurfactant that is generally used in emulsion polymerization, in orderto improve the particle stability. The surfactant may be exemplified bythe above-described anionic surfactants, nonionic surfactants, cationicsurfactants, other reactive surfactants or the like, and these can beused individually or in combination of two or more species.

The amount of the surfactant to be used is not particularly limited.However, when the amount of use increases, the particles formed onlyfrom the copolymerizable monomers (B) consisting of a monomer having anα,β-monoethylenically unsaturated group and other copolymerizablemonomer(s) may be generated, and thus the surfactant is used typicallyin an amount of 0.02 to 5% by weight based on the total weight ofcopolymerizable monomers (B).

Furthermore, in the case of incorporating a third component, it ispreferable to use it as mixed with copolymerizable monomers (B).

The solvent dispersion of a composite resin of the invention may includethose solvent dispersions having the resin dispersed in various solventsas well as those having the resin partly dissolved therein.

Also, the resin liquid of the invention can be used as a resin liquid inwhich after removing the dissolving agent, the resin is dissolved anddispersed in an arbitrary solvent. A resin liquid in which the resin isdissolved or dispersed, and a resin liquid in which the resin isdispersed in a resin liquid are all embodiments of the solventdispersion of a composite resin of the invention and are included in theinvention.

A resin liquid in which the resin obtained by carrying out a reaction inan organic solvent is dissolved or dispersed therein, and a resin liquidin which the resin is dispersed in a resin liquid are also embodimentsof the resins of the invention and are included in the invention.

Among the solvent dispersions of a composite resin of the invention,those having active hydrogen and/or a hydroxyl group, which containhydroxyethyl acrylate, 2-hydroxyethyl (meth)acrylate, acrylic acid,methacrylic acid and the like as the constituting unit, can be used witha curing agent which can react with the active hydrogen and/or hydroxylgroup. For example, when such a solvent dispersion is mixed with acuring agent having an isocyanate group in the molecule, which is one ofthose curing agents which can react with active hydrogen and/or ahydroxyl group, the solvent dispersion can be used as a coatingmaterial, a primer or an adhesive, which has urethane bonds.

For the curing agent having an isocyanate group in the molecule, whichcan react with active hydrogen and/or a hydroxyl group, the followingcan be used: the adducts obtained from one or two or more species ofaromatic diisocyanates such as phenylenediisocyanate,tolylenediisocyanate, xylylenediisocyanate anddiphenylmethanediisocynate, aliphatic diisocyanates such ashexamethylenediisocyanate, trimethylhexamethylenediisocyanate andlysinediisocyanate, alicyclic diisocyanates such asisophorondiisocyanate and dicyclohexylmethanediisocyanate, and otherisocyanate compounds, and from polyhydric alcohols, including dihydricalcohols such as ethylene glycol, propylene glycol, xylene glycol andbutylene glycol, and trihydric alcohols such as glycerin,trimethylolpropane and trimethylolethane; the adducts of theabove-mentioned isocyanate compounds and of low molecular weightpolyester resins having a functional group which can react with anisocyanate group, or water; Biuret compounds; polymers of differentdiisocyantes; those having the isocyanate group blocked with a knownblocking agent such as lower monohydric alcohols and methyl ethylketoxime; and the like. Also, in the case of using isocyanateprepolymers, it is possible to add an external catalyst such as, forexample, dibutyltin dilaurate or triethylamine.

Furthermore, for a system containing water in the solvent, those systemsin which the isocyanate group treated with a blocking agent such asoximes, lactams or phenols is present in water, for example, Takenate WBSeries (manufactured by Mitsui Takeda Chemicals, Inc.), Elastron BNSeries (Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, can be used.

Also it is possible to use as the curing agent, those amino resins whichare resins synthesized from at least one of melamine, urea,benzoguanamine, glycoluryl and the like, and from formaldehyde, and theamino resins resulting from alkyl etherification of all or part of themethylol groups by means of lower alcohols such as methanol, ethanol,propanol, isopropanol, butanol and isobutanol.

In a system containing water in the solvent, oxazoline compounds can beused as the curing agent. For the aforementioned curing agent,2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline,2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline,2-isopropenyl-4-methyl-2-oxazoline or the like can be used as the curingagent.

The solvent dispersion of a composite resin of the invention and thecuring agent which can react with active hydrogen and/or a hydroxylgroup, can be used at any ratio.

When the curing agent which can react with active hydrogen and/or ahydroxyl group is a curing agent having an isocyanate group, the mixingratio, as an equivalent ratio of active hydrogen and the isocyanategroup, is preferably in the range of 0.5:1.0 to 1.0:0.5, and morepreferably in the range of 0.8:1.0 to 1.0:0.8.

Also, when the curing agent which can react with active hydrogen and/ora hydroxyl group is an amino resin, the ratio of (solvent dispersion ofa composite resin of the invention/amino resin), as a ratio by weight ofthe solid components, is preferably in the range of 95/5 to 20/80, andmore preferably in the range of 90/10 to 60/40.

When the curing agent which can react with active hydrogen and/or ahydroxyl group is an oxazoline compound, the ratio of (composition ofthe invention/oxazoline compound), as a ratio by weight of the solidcomponents, is preferably in the range of 95/5 to 20/80, and morepreferably in the range of 90/10 to 60/40.

A solvent dispersion which is mixed with the above-described curingagents can be directly applied and cured, but it can be also combinedwith a reactive catalyst, if necessary.

The above-obtained solvent dispersion of a composite resin of theinvention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, can contain, if desired, ingredients includingcolorants, including organic pigments such as azo pigments andphthalocyanine blue, dyes such as azo dyes and anthraquinone dyes, andinorganic pigments such as titanium oxide, molybdenum and carbon black;various stabilizers such as an antioxidant, a weather resistantstabilizer and a heat resistant preventives; an antifoaming agent, athickener, a dispersant, a surfactant, an antifungal agent, anantibacterial agent, an antiseptic, a catalyst, a filler, a wax, anantiblocking agent, a plasticizer, a leveling agent and the like.

The method of applying the solvent dispersion of a composite resin ofthe invention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, is not particularly limited, but it ispreferably carried out by spray coating. For example, the solventdispersion can be applied by spraying strongly onto the surface to becoated with a spray gun. Usually, application can be easily carried outat room temperature. Further, the drying method after application is notparticularly limited, and it is possible to carry out drying by anyappropriate method such as natural drying and forced drying underheating.

Furthermore, the solvent dispersion of a composite resin of theinvention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, can be suitably used, due to its features, asan overcoat, a primer or an adhesive, for molded articles made ofpolyolefin such as polyethylene and polypropylene, an olefinic copolymersuch as an ethylene-propylene copolymer, an ethylene-butene copolymer, apropylene-butene copolymer and an ethylene-propylene-butene copolymer;and molded articles made of polypropylene and a rubber component;polyamide resins, unsaturated polyesters, polycarbonate, epoxy resins,urethane resins, steel plates, electroplated steel plates and the like.Also, for overcoating, coating materials comprising urethane coatingmaterials, polyester coating materials, melamine coating materials orepoxy coating materials as the main component can be used, in order toimprove adherence to various surfaces to be coated and also to form acoating film having excellent distinctness of image.

In addition, the solvent dispersion of a composite resin of theinvention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, is used, due to its features, as an adhesive ora heat sealing agent between metals, between polyolefins, or betweenmetal and polyolefin and exhibits excellent adhesive performance andcohesive performance, without having tackiness in the coating film.Also, upon heat sealing, the solvent dispersion of a composite resin ofthe invention exhibits its performance at low temperatures. Thedispersion can be also used as an adhesive for PTP packaging and anadhesive for laminates.

In addition to the above-described applications, the solvent dispersionof a composite resin of the invention, or the solvent dispersion of acomposite resin of the invention mixed with a curing agent which canreact with active hydrogen and/or a hydroxyl group, can be used, due toits features, as a mixture with solvent-type thermoplastic acrylic resincoating materials, solvent-type thermosetting acrylic resin coatingmaterials, acryl-modified alkyd resin coating materials, epoxy resincoating materials, polyurethane resin coating materials, and melamineresin coating materials.

The above-obtained solvent dispersion of a composite resin of theinvention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, can be used as a binder resin for colorants,including organic pigments such as an azo pigment and a phthalocyanineblue, dyes such as an azo dye and an anthraquinone dye, and inorganicpigments such as titanium oxide, molybdenum and carbon black; andinorganic chemicals such as aluminum oxide, calcium carbonate, calciumhydroxide, magnesium hydroxide, silica and barium titanate.

The film obtained by applying the above-obtained solvent dispersion of acomposite resin of the invention, or the solvent dispersion of acomposite resin of the invention mixed with a curing agent which canreact with active hydrogen and/or a hydroxyl group, on a releasable filmor the like and then peeling off therefrom, is excellent in flexibility,impact resistance, elasticity, transparency, gloss, blocking resistanceand designability. Thus, the film can be used in applications such asclothing materials, various packaging materials, medical instruments,personal hygienic goods, various molded products, display layermaterials for display panel and optical materials. Also, since it ispossible to control light transmittance by elasticity and also toscatter transmitted light, the film can be used as an optical materialsuch as a light-shielding film or a light-controlling film.

Furthermore, the above-obtained solvent dispersion of a composite resinof the invention, or the solvent dispersion of a composite resin of theinvention mixed with a curing agent which can react with active hydrogenand/or a hydroxyl group, can be used as a primer for strippable paintsand traffic paints.

EXAMPLES

Hereinafter, the invention is more specifically explained with referenceto Examples, but is not limited to these Examples.

Example 1 Preparation of Propylene-Based Elastomer

To a 2-liter autoclave sufficiently purged with nitrogen, 950 cm³ ofhexane and 50 g of 1-butene were introduced, and 1 mmol oftriisobutylaluminum was added. After elevating the temperature to 70°C., propylene and ethylene were supplied thereto to increase the totalpressure to 0.69 MPaG. Then, 0.30 mmol of methylaluminoxane and 0.001mmol (in terms of Zr atoms) ofrac-dimethylsilylene-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride were added, and while maintaining the total pressure at 0.69MPaG by continuously supplying propylene and ethylene at a molar ratioof 95:5, polymerization was carried out for 30 minutes. Afterpolymerization, the autoclave was vented, and the polymer was recoveredin a large amount of methanol and dried under reduced pressure at 110°C. for 12 hours to yield 28.0 g of a propylene-based elastomer (I-1).The polylmerization activity was 56 kg·polymer/mmol of Zr·hr.

Preparation of Solvent Dispersion of a Composite Resin

A four-necked flask equipped with a stirrer, a thermometer, a refluxcondenser and a nitrogen-inlet tube was charged with 100 parts by weightof the propylene-based elastomer (1-1) obtained by the method of Example1 above and 250 parts by weight of Shellsol TG as an organic solvent.The mixture was heated to 130° C. under purging with nitrogen.Subsequently, a liquid mixture comprising 45 parts by weight of methylmethacrylate, 20 parts by weight of isobutyl methacrylate, 14 parts byweight of ethyl acrylate, 15 parts by weight of Placcel FM-3, 5 parts byweight of hydroxyethyl methacrylate, and 1 part by weight of methacrylicacid as a polymerizable monomer and 1 part by weight of di-tert-butylperoxide (hereinafter, abbreviated to PBD) as a polymerizationinitiator, was fed to the flask over 4 hours. After 30 minutes fromcompletion of feeding, the temperature was elevated to 135° C., andafter further 30 minutes, 0.5 part by weight of PBD was added. After onemore hour, 50 parts by weight of Shellsol TG was added, andsimultaneously 0.5 part by weight of PBD was added. After 1 hour fromthis addition of PBD, the temperature was elevated to 160° C., andsimultaneously 6 parts by weight of PBD was added. Further after onehour, 2 parts by weight of PBD was added, and after another hour, 2parts by weight of PBD was added again to carry out the reaction. Afteraddition of PBD, the reaction mixture was left to stand for 2 hours toundergo the reaction, and thus a solvent dispersion of a composite resinwas obtained.

Shellsol TG used above is an isoparaffin-based organic solventmanufactured by Shell Chemicals Japan, Ltd., and Placcel FM-3 used as apolymerizable monomer is unsaturated fatty acid hydroxyalkylether-modified ε-caprolactone manufactured by Daicel ChemicalIndustries, Ltd.

Example 2 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 1 was carried out, except that during thepreparation of solvent dispersion of a composite resin, the solvent wasall replaced with methylcyclohexane, the temperature in the system wasmaintained at 97° C. for all processes, and the polymerization initiatorwas changed to tert-butylperoxy-2-ethylhexanoate (hereinafter,abbreviated to PBO), to obtain a solvent dispersion of a compositeresin.

Example 3 Preparation of Solvent Dispersion of a Composite Resin

A four-necked flask equipped with a stirrer, a thermometer, a refluxcondenser and a nitrogen inlet tube was charged with 100 parts by weightof the propylene-based elastomer (I-1) obtained by the method of Example1 above, and 200 parts by weight of Shellsol TG as an organic solvent.The mixture was heated to 130° C. under purging with nitrogen.Subsequently, a resin solution for dropwise addition obtained by thebelow-described method was added thereto dropwise over 1 hour, and aftercompletion of the dropwise addition, the temperature inside the systemwas elevated to 140° C., and 6 parts by weight of PBD was added. Afterone hour, 2 parts by weight of PBD was added, and after another hour, 2parts by weight of PBD was added again to carry out the reaction. Afteraddition of PBD, the reaction mixture was left to stand for 2 hours toundergo the reaction, and thus a solvent dispersion of a composite resinwas obtained.

Resin Solution for Dropwise Addition

A four-necked flask equipped with a stirrer, a thermometer, a refluxcondenser and a nitrogen inlet tube was charged with 70 parts by weightof xylene and 30 parts by weight of Anone. The mixture was heated to100° C. under purging with nitrogen. Subsequently, a liquid mixturecomprising 45 parts by weight of methyl methacrylate, 14 parts by weightof ethyl acrylate, 20 parts by weight of isobutyl methacrylate, 5 partsby weight of hydroxyethyl acrylate, 15 parts by weight of Placcel FM-3,1 part by weight of methacrylic acid and 1 part by weight of PBO, wasfed thereto over 4 hours. After 30 minutes from completion of feeding,the temperature was elevated to 110° C., and after further 30 minutes,0.5 part by weight of PBO was added. Further after 1 hour from thisaddition of PBO, 0.5 part by weight of PBO was added. After the additionof PBO, the reaction mixture was left to stand for 2 hours to undergothe reaction, and thus a resin solution was obtained.

Example 4 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 3 was carried out, except that during thepreparation of solvent dispersion of a composite resin, the solvent wasall replaced with methylcyclohexane, the temperature in the system wasmaintained at 97° C. for all processes, and the polymerization initiatorwas changed to PBO, to obtain a solvent dispersion of a composite resin.

Example 5 Preparation of Solvent Dispersion of a Composite Resin

A four-necked flask equipped with a stirrer, a thermometer, a refluxcondenser and a nitrogen inlet tube was charged with 100 parts by weightof the propylene-based elastomer (1-1) obtained by the method of Example1 above and 150 parts by weight of Shellsol TG. The mixture was heatedto 130° C. under purging with nitrogen. Subsequently, 3 parts by weightof Placcel FM-3 as a polymerizable monomer having a functional group wasadded and dispersed thereto, and then 3 parts by weight of PBD was addedto carry out the reaction for 2 hours. Then, 115 parts by weight ofShellsol TG was added, and a resin in which the thermoplastic elastomeris partly modified with a functional group was obtained. Subsequently,while maintaining the temperature in the system at 130° C., a liquidmixture comprising 45 parts by weight of methyl methacrylate, 14 partsby weight of ethyl acrylate, 20 parts by weight of isobutylmethacrylate, 5 parts by weight of 2-hydroxyethyl methacrylate, 15 partsby weight of Placcel FM-3, 1 part by weight of methacrylic acid as thepolymerizable monomer and 1 part by weight of PBD, was fed over 4 hours.After 30 minutes from completion of feeding, the temperature waselevated to 135° C., and after further 30 minutes, 50 parts by weight ofShellsol TG was added, and simultaneously 0.7 part by weight of PBD wasadded. Further after one hour, 0.7 part by weight of PBD was added.After 30 minutes from this addition of PBD, the temperature was elevatedto 160° C., and the reaction mixture was left to stand for another onehour to undergo the reaction. Thus, a solvent dispersion of a compositeresin was obtained.

Example 6 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 5 was carried out, except that during thepreparation of solvent dispersion of a composite resin, the solvent wasall replaced with methylcyclohexane, the temperature in the system wasmaintained at 97° C. for all processes, and the polymerization initiatorwas changed to PBO, to obtain a solvent dispersion of a composite resin.

Example 7 Preparation of Propylene-Based Elastomer

In the preparation of propylene-based elastomer of Example 1,copolymerization of propylene, 1-butene and ethylene was carried out inthe same manner as in Example 1, except that 60 g of 1-butene wasintroduced, and thus 24.1 g of propylene-based elastomer (1-2) wasobtained. The polymerization activity was 48 kg·polymer/mmol of Zr·hr.

Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 1 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(I-2) obtained in Example 7 above, to obtain a solvent dispersion of acomposite resin.

Example 8 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 3 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(I-2) obtained in Example 7 above, to obtain a solvent dispersion of acomposite resin.

Example 9 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 5 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(I-2) obtained in Example 7 above, to obtain a solvent dispersion of acomposite resin.

Example 10 Preparation of Propylene-Based Elastomer

To a 2-liter autoclave sufficiently purged with nitrogen, 900 cm³ ofhexane and 90 g of 1-butene were introduced, and 1 mmol oftriisobutylaluminum was added. After elevating the temperature to 70°C., propylene and ethylene were supplied thereto to increase the totalpressure to 0.69 MPaG. Then, 0.30 mmol of methylaluminoxane and 0.001mmol (in terms of Zr atoms) ofrac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride were added, and while maintaining the total pressure at 0.69MPaG by continuously supplying propylene, polymerization was carried outfor 30 minutes. After polymerization, the autoclave was vented, and thepolymer was recovered in a large amount of methanol and dried underreduced pressure at 110° C. for 12 hours to yield 39.7 g of apropylene-based elastomer (II). The polymerization activity was 79kg·polymer/mmol of Zr·hr.

Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 1 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Example 11 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 2 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Example 12 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 3 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Example 13 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 4 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Example 14 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 5 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Example 15 Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 6 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(II) obtained in Example 10 above, to obtain a solvent dispersion of acomposite resin.

Examples 16 to 24

To each of the solvent dispersions of a composite resin obtained inExamples 1, 3, 5, 7 to 10, 12 and 14, D-170HN (Mitsui Takeda Chemicals,Inc., product name) was incorporated as a curing agent to give a resinsolution. The amount of mixing was 2.6 parts by weight of the curingagent relative to 100 parts by weight of the solvent dispersion of acomposite resin for Examples 1, 3, 7, 8, 10 and 12, and 3.1 parts byweight of the curing agent relative to 100 parts by weight of thesolvent dispersion of a composite resin for Examples 5, 9 and 14.

Examples 25 to 33

To each of the dispersions of a composite resin obtained in Examples 1,3, 5, 7 to 10, 12 and 14, 30% by weight of titanium oxide pigment(Tipaque-CR93 (Ishihara Sangyo Co., Ltd., product name)) and 40 parts byweight of an organic solvent mixture at a ratio of xylene/toluene/methylisobutyl ketone=1/1/1 relative to each resin content were added, toobtain a paint resin.

Example 34

Five hundred grams of the resin solution obtained in Example 6, 500 g ofion-exchanged water and 5 g of potassium oleate (Kanto Chemical Co.,Inc.) were mixed for 30 minutes with stirring at a rotation speed of10,000 rpm. Next, 1 g of polyacrylic acid was added and mixed withstirring to obtain an emulsion. Methylcyclohexane in the thus obtainedemulsion was removed under reduced pressure in an evaporator to obtain asolvent dispersion of a composite resin.

Example 35

Synthesis was carried out by the same method as in Example 6, exceptthat the polymerizable monomer was changed to 49 parts of methylmethacrylate, 21 parts of ethyl acrylate, 14 parts of isobutylmethacrylate, 14 parts of 2-hydroxyethyl methacrylate, 21 parts ofPlaccel FM-3 and 21 parts of methacrylic acid, to obtain a resinsolution. To the resulting resin solution, 300 parts of butyl cellosolvewas added and dissolved therein, and then neutralization withtriethylamine was carried out to a theoretical extent of 100%. Then, thesolvent was removed under heating at 100° C. and reduced pressure. Thiswas adjusted with deionized water to contain 40% of non-volatilecomponents, and thus a solvent dispersion of a composite resin wasobtained.

Example 36

To a pressurized kneader, 100 parts of the propylene-based elastomer(1-1) described in Example 1, 10 parts of maleic anhydride graftedpolyethylene (maleic acid content: 3.3 wt %, weight-average molecularweight: 2700, density: 0.94 g/cm³), which acts as a dispersant under theaction of basic substances, and 5 parts of oleic acid were introduced,and the mixture was melt-kneaded at 140° C. for 30 minutes. Next, 20parts of alkaline water in which potassium hydroxide (basic substance)which is necessary in neutralizing all of the carboxylic acids of maleicanhydride grafted polyethylene and oleic acid was dissolved, wasintroduced under pressure for 5 minutes using a pump connected to thekneader. The pressure inside the kneader reached 3 kg/cm³G. Mixing wascontinued for 30 minutes thereafter, then the kneader was cooled to 60°C., and the content was removed. The content was a white solid. Tenparts of the white solid was introduced in 10 parts of water, and themixture was stirred with a turbine-blade stirrer and then filteredthrough a 100-mesh wire gauze. The residues were neglected.

A reactor was charged with 140 parts of the above-obtained emulsion and152 parts of deionized water, and the temperature was elevated to 80° C.under a nitrogen atmosphere. Apart from this, an emulsified mixture wasprepared by emulsifying 15 parts of styrene, 15 parts of 2-ethylhexylacrylate, 3 parts of 2-hydroxyethyl methacrylate and 0.3 part of benzoylperoxide in 12 parts of deionized water using 0.12 part of sodiumdodecylbenzenesulfonate. This emulsified mixture was added dropwise tothe reactor over 3 hours, and then the system was maintained at the sametemperature for 4 hours to complete polymerization. Thus, a solventdispersion of a composite resin was obtained.

Comparative Example 1 Preparation of Propylene-Based Elastomer

To a 500 cm³-flask, 250 cm³ of n-decane, 1.25 mmol oftriisobutylaluminum, 0.15 mmol of diphenyldimethoxysilane, and 0.025mmol (in terms of titanium atoms) of a titanium catalyst supported onmagnesium chloride were added, the temperature was elevated to 70° C.,10 dm³/hr of ethylene, 120 dm³/hr of propylene, 80 dm³/hr of 1-buteneand 10 dm³/hr of hydrogen were introduced continuously to the solventunder normal pressure, and polymerization was carried out at 70° C. for30 minutes. Polymerization was carried out in the solution state.Polymerization was stopped by addition of isobutyl alcohol, and theentire amount of the polymer was precipitated in a large quantity ofmethanol and dried overnight under vacuum at 120° C. to yield 15 g of apropylene-based elastomer (III).

Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 1 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(III) obtained in the above Comparative Example 1, to obtain a solventdispersion of a composite resin.

Comparative Example 2 Preparation of Solvent Dispersion of a CompositeResin

The same method as in Example 3 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(III) obtained in the above Comparative Example 1, to obtain a solventdispersion of a composite resin.

Comparative Example 3 Preparation of Solvent Dispersion of a CompositeResin

The same method as in Example 5 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(III) obtained in the above Comparative Example 1, to obtain a solventdispersion of a composite resin.

Comparative Example 4 Preparation of Propylene-Based Elastomer

To a 2-liter autoclave sufficiently purged with nitrogen, 830 ml ofhexane and 100 g of 1-butene were introduced, and 1 mmol oftriisobutylaluminum was added. After elevating the temperature to 70°C., propylene was supplied thereto to increase the total pressure to0.69 MPaG. Then, 1 mmol of triethylaluminum and 0.005 mmol (in terms oftitanium atoms) of a titanium catalyst supported on magnesium chloridewere added, and while maintaining the total pressure at 0.69 MPaG bycontinuously supplying propylene, polymerization was carried out for 30minutes. After polymerization, the autoclave was vented, and the polymerwas recovered in a large amount of methanol and dried under reducedpressure at 110° C. for 12 hours to yield 33.7 g of a propylene-basedelastomer (IV).

Preparation of Solvent Dispersion of a Composite Resin

The same method as in Example 10 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(IV) obtained in the above Comparative Example 4, to obtain a solventdispersion of a composite resin.

Comparative Example 5 Preparation of Solvent Dispersion of a CompositeResin

The same method as in Example 12 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(IV) obtained in the above Comparative Example 4, to obtain a solventdispersion of a composite resin.

Comparative Example 6 Preparation of Solvent Dispersion of a CompositeResin

The same method as in Example 14 was carried out, except that during thepreparation of solvent dispersion of a composite resin, thepropylene-based elastomer was changed to the propylene-based elastomer(IV) obtained in the above Comparative Example 4, to obtain a solventdispersion of a composite resin.

<<Evaluation>>

Evaluation of propylene-based elastomers (I) and (II)

Each of the obtained propylene-based elastomers (I) and (II) wasevaluated by the below-described methods. The results were shown inTable 1.

<Composition>

It was determined using ¹³C-NMR.

<Intrinsic Viscosity [η]>

It was measured in decalin at 135° C.

<Molecular Weight Distribution (Mw/Mn)>

It was measured as follows, using a GPC-150C manufactured by MilliporeCorp. The separating column was TSK GNH HT, and the column size was 27mm in diameter and 600 mm in length. The column temperature was set at140° C., and the mobile phase used was o-dichlorobenzene (Wako PureChemical Industries, Ltd.) and 0.025% by weight of BHT (TakedaPharmaceutical Co., Ltd.) as an antioxidant. The flow rate was 1.0cm³/min. The sample concentration was 0.1% by mass, the amount of thesample injected was 0.5 cm³, and the detector used was a differentialrefractometer. For the standard polystyrene, products of TosohCorporation were used for the molecular weights of Mw<1000 and Mw>4×10⁶,and a product of Pressure Chemical Co. was used for the molecular weightof 1000<Mw<4×10⁶.

<Melting Point (Tm)>

About 5 mg of the sample was placed in an aluminum pan, and thetemperature was elevated to 200° C. at a rate of 10° C./min, maintainedat 200° C. for 5 minutes, lowered to room temperature at a rate of 20°C./min and subsequently elevated at a rate of 10° C./min, at which timean endothermic curve was determined. The measurement was made using aDSC-7 type apparatus manufactured by PerkinElmer, Inc.

TABLE 1 Propylene-based Elastomer I-1 I-2 II III IV CompositionPropylene 69.6 65.0 73.6 68.2 74.7 (mol %) 1-Butene 15.3 20.0 26.4 21.525.3 Ethylene 15.1 15.0 10.3 Intrinsic Viscosity [η] (dl/g) 2.40 2.301.80 2.00 1.89 Molecular Weight Distribution 2.1 2.2 2.0 5.1 3.5 (Mw/Mn)Melting Point (Tm) (° C.) 72.2 64.5 88.4 78.3 110.0

Evaluation of the resulting solvent dispersions of composite resin

Each of the resulting solvent dispersions of a composite resin wasevaluated by the below-described method. The results were shown in Table2 and Table 3.

<Stability of Resin Solution>

The resin composition solutions obtained in Examples 1 to 15, 34 to 36and Comparative Examples 1 to 6 were allowed to stand at roomtemperature and at 40° C. for 1 month, respectively and the states ofthe solutions were evaluated. After elapse of 1 month, the resincomposition solution, which was observed to be free from separation andprecipitation was evaluated as ◯, the resin composition solution, whichwas observed to have separation and/or precipitation but was easilydispersed by stirring, was evaluated as Δ and the resin composition,which was observed to have separation and/or precipitation and was noteasily dispersed by stirring, was evaluated as x.

<Sprayability of Resin Solution>

The resin composition solution obtained in each of the Examples andComparative Examples was sprayed using a coating gun (Wider Spray Gunmanufactured by Iwata Tosoki Kogyo Co. (tradename; W-88-13H5G)) at anatomization pressure of 4 kg/cm², with a nozzle opening per rotation andthe temperature in the coating booth being 30° C., and whether thereexists generation of stringiness or not was observed. When nostringiness was observed, the resin composition solution was evaluatedas ◯. When at least one string was observed, it was evaluated as x.

<Evaluation of Coating Film>

(1) Evaluation with Polypropylene

The resin solutions obtained in Examples 1 to 36 were diluted with thesame solvent used in the preparation thereof and controlled to have adropping time of 15±2 seconds by using Ford cup No. 4 at 25° C.Subsequently, the above-described solution was applied by spraying on asquare plate made of polypropylene (Sumitomo Mitsui Polyolefin Co.,Ltd., product name; J700) having the surface wiped with isopropylalcohol, such that the film thickness after drying would be 10 μm, andafter drying at 80° C. for 20 minutes, a coating film was obtained. Withrespect to this coating film, the cross-cut peel and tackiness of thecoating film surface were evaluated by finger touch. Furthermore, awhite topcoat paint was applied on the above-described coating film suchthat the film thickness after drying would be 20 μm, and the plate wasleft to stand at room temperature for 10 minutes and was subjected tobaking in an oven at 80° C. for 20 minutes to give a coating film. Thiscoating film was subjected to the cross-cut peel test. Also, the weatherresistance test was carried out, and the gloss retention after the testand cross-cut peel were evaluated.

Moreover, with respect to Examples 25 to 33, 0.2% of a UV absorber(TINUVIN 327) and 0.2% of an antioxidant (IRGANOX 1330) relative to theresin content were added, respectively, and at the same time, a curingagent was mixed to the amounts described in Examples 16 to 24. Thus, theresin solutions were applied by the above-described method to givecoating films. These coating films were subjected to evaluation for thecross-cut peel and tackiness of the coating film surface by fingertouch. Also, the weather resistance test was carried out, and the glossretention after the test and cross-cut peel were evaluated.

(2) Evaluation with Olefinic Thermoplastic Elastomer (Tafmer)

The resin solutions obtained in Examples 1 to 36 were diluted with thesame solvent used in the preparation thereof and controlled to have adropping time of 15±2 seconds by using Ford cup No. 4 at 25° C.Subsequently, the above-described solution was applied by spraying on asquare plate made of olefinic thermoplastic elastomer (Mitsui Chemicals,Inc., product name; Tafmer A4070) having the surface wiped withisopropyl alcohol such that the film thickness after drying would be 5μm, and after drying at 80° C. for 20 minutes, a coating film wasobtained. This coating film was subjected to the cross-cut peel test.Furthermore, a white topcoat paint was applied on the above-describedcoating film such that the film thickness after drying would be 10 μm,and the plate was left to stand at room temperature for 10 minutes andwas subjected to baking in an oven at 80° C. for 20 minutes to give acoating film. This coating film was subjected to the cross-cut peeltest.

(3) Evaluation with Olefinic Thermoplastic Elastomer (Milastomer)

The resin solutions obtained in Examples 1 to 36 were diluted with thesame solvent used in the preparation thereof and controlled to have adropping time of 15±2 seconds by using Ford cup No. 4 at 25° C.Subsequently, the above-described solution was applied by spraying on asquare plate made of olefinic thermoplastic elastomer (Mitsui Chemicals,Inc., product name; Milastomer 8030) having the surface wiped withisopropyl alcohol such that the film thickness after drying would be 5μm, and after drying at 80° C. for 20 minutes, a coating film wasobtained. This coating film was subjected to the cross-cut peel test.Furthermore, a white topcoat paint was applied on the above-describedcoating film such that the film thickness after drying would be 10 μm,and the plate was left to stand at room temperature for 10 minutes andwas subjected to baking in an oven at 80° C. for 20 minutes to give acoating film. This coating film was subjected to the cross-cut peeltest.

Here, the topcoat paint used in the above was a mixture of a main agentin which 0.2% of a UV absorber (TINUVIN327) relative to the resincontent, 0.2% of an antioxidant (IRGANOX1330) relative to the resincontent, and 30% of a titanium oxide pigment (Tipaque-CR93 (IshiharaSangyo Co., Ltd., tradename)) relative to the resin content aredispersed in Olester Q186 (Mitsui Chemicals, Inc., tradename,non-volatile content: 50%, hydroxyl value: 30 KOH mg/g), and a curingagent containing NCO, MT Olester NM89-50G (Mitsui Takeda Chemicals,Inc., tradename, non-volatile content: 50%, NCO %: 6%), to the ratio ofOH/NCO=0.95.

Cross-Cut Peel Test

According to the cross-cut peel test described in JIS-K-5400, a specimenhaving grid cell marks was prepared, and Cellotape (registered mark)(Nichiban Co., Ltd.) was adhered on the grid cells and then peeled offby pulling rapidly in the direction of 90°. Evaluation was made bycounting the number of unpeeled grid cells among the 100 grid cells.

In addition, for the coating film evaluation item (1), the sameevaluation was made by using gummed tape, in addition to Cellotape(registered mark). The cross-cut peel test using the gummed tape wascarried out such that the peel test was carried out 10 times on the sameplace, and the number of unpeeled grid cells was counted. Also, thecross-cut peel test after the weather resistance test was carried outusing Cellotape (registered mark) only.

Weather Resistance Test

According to the method of an accelerated weather resistance test asdescribed in JIS-K-5400, evaluation was made by a sunshine carbon arclamp method. By means of a 60° specular gloss measured after exposurefor 500 hours (JIS-K-5400), the retention of the measured value wascalculated by the formula: retention (%)=(specular gloss aftertest)/(initial specular gloss)×100. Those having a gloss retention of80% or more and no color change were rated ◯, those having a glossretention of 60% or more to less than 80% were rated A and those havinga gloss retention of less than 60% were rated x.

<Heat Seal Test>

The resin solutions obtained in Examples 1 to 15, 34 to 36 andComparative Examples 1 to 6 were diluted with the same solvent used inthe preparation thereof to have a non-volatile content of 10%.Subsequently, the above-described solution was applied on aluminum foilwith a bar coater such that the film thickness after drying would be 2μm, dried in the air, and then heated in an air oven set at 200° C. for20 seconds, to give a uniform and transparent coating foil. This coatingfoil and a polypropylene sheet (Tohcello Co., Ltd. #500T-T) were heatsealed according to the method of JIS-Z-1707, by applying a pressure of0.098 MPa at 120° C. for 1 sec, and thus a specimen was obtained. Thespecimen was cut into rectangles of 15 mm width, and the 180° peel (peeloff) test was carried out at room temperature. Those having a peelstrength of 1000 g/15 mm or more were rated ◯, those having a peelstrength of 500 or more to less than 1000 g/15 mm were rated A, andthose having a peel strength of less than 500 g/15 mm were rated x.

TABLE 2 Example 1 2 3 4 5 6 7 8 9 10 11 12 Stability of resin solution ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Sprayability ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ PolypropyleneWithout Cross-cut 100 100 100 100 100 100 100 100 100 100 100 100topcoat peel test (Cellotape) Cross-cut 100 100 100 100 100 100 100 100100 100 100 100 peel test (gummed tape) Coating ab- ab- ab- ab- ab- ab-ab- ab- ab- ab- ab- ab- tack sent sent sent sent sent sent sent sentsent sent sent sent With Cross-cut 100 100 100 100 100 100 100 100 100100 100 100 topcoat peel test (Cellotape) Cross-cut 100 100 100 100 100100 100 100 100 100 100 100 peel test (gummed tape) Gloss ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ retention after weather resistance test Cross-cut 100 100 100100 100 100 100 100 100 100 100 100 peel after weather resistance testTafmer Without Cross-cut 100 100 100 100 100 100 100 100 100 100 100 100topcoat peel test With Cross-cut 100 100 100 100 100 100 100 100 100 100100 100 topcoat peel test Milastomer Without Cross-cut 100 100 100 100100 100 100 100 100 100 100 100 topcoat peel test With Cross-cut 100 100100 100 100 100 100 100 100 100 100 100 topcoat peel test Peeling off ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Example 13 14 15 16 17 18 19 20 21 22 23 24Stability of resin solution ∘ ∘ ∘ — — — — — — — — — Sprayability ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Polypropylene Without Cross-cut 100 100 100 100 100 100100 100 100 100 100 100 topcoat peel test (Cellotape) Cross-cut 100 100100 100 100 100 100 100 100 100 100 100 peel test (gummed tape) Coatingab- ab- ab- ab- ab- ab- ab- ab- ab- ab- ab- ab- tack sent sent sent sentsent sent sent sent sent sent sent sent With Cross-cut 100 100 100 100100 100 100 100 100 100 100 100 topcoat peel test (Cellotape) Cross-cut100 100 100 100 100 100 100 100 100 100 100 100 peel test (gummed tape)Gloss ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ retention after weather resistance testCross-cut 100 100 100 100 100 100 100 100 100 100 100 100 peel afterweather resistance test Tafmer Without Cross-cut 100 100 100 100 100 100100 100 100 100 100 100 topcoat peel test With Cross-cut 100 100 100 100100 100 100 100 100 100 100 100 topcoat peel test Milastomer WithoutCross-cut 100 100 100 100 100 100 100 100 100 100 100 100 topcoat peeltest With Cross-cut 100 100 100 100 100 100 100 100 100 100 100 100topcoat peel test Peel off ∘ ∘ ∘ — — — — — — — — —

TABLE 3 Example 25 26 27 28 29 30 31 32 33 34 35 36 Stability of resinsolution — — — — — — — — — ∘ ∘ ∘ Sprayability ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘Polypropylene Without Cross-cut 100 100 100 100 100 100 100 100 100 100100 100 topcoat peel test (Cellotape) Cross-cut 100 100 100 100 100 100100 100 100 100 100 100 peel test (gummed tape) Coating ab- ab- ab- ab-ab- ab- ab- ab- ab- ab- ab- ab- tack sent sent sent sent sent sent sentsent sent sent sent sent With Cross-cut 100 100 100 100 100 100 100 100100 100 100 100 topcoat peel test (Cellotape) Cross-cut 100 100 100 100100 100 100 100 100 100 100 100 peel test (gummed tape) Gloss ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ retention after weather resistance test Cross-cut 100 100100 100 100 100 100 100 100 100 100 100 peel after weather resistancetest curing Cross-cut 100 100 100 100 100 100 100 100 100 — — — agentpeel test introduced (Cellotape) without Cross-cut 100 100 100 100 100100 100 100 100 — — — topcoat peel test (gummed tape) Coating ab- ab-ab- ab- ab- ab- ab- ab- ab- — — — tack sent sent sent sent sent sentsent sent sent Gloss ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ — — — retention after weatherresistance test Cross-cut 100 100 100 100 100 100 100 100 100 — — — peelafter weather resistance test Tafmer Without Cross-cut 100 100 100 100100 100 100 100 100 100 100 100 topcoat peel test With Cross-cut 100 100100 100 100 100 100 100 100 100 100 100 topcoat peel test MilastomerWithout Cross-cut 100 100 100 100 100 100 100 100 100 100 100 100topcoat peel test With Cross-cut 100 100 100 100 100 100 100 100 100 100100 100 topcoat peel test Peel off — — — — — — — — — ∘ ∘ ∘ ComparativeExample 1 2 3 4 5 6 Stability of resin solution ∘ ∘ ∘ ∘ ∘ ∘ Sprayability∘ ∘ ∘ ∘ ∘ ∘ Polypropylene Without Cross-cut 100  100  100 100  100 100topcoat peel test (Cellotape) Cross-cut 95 93  95 95  90  97 peel test(gummed tape) Coating present present present slightly slightly slightlytack present present present With Cross-cut 95 95 100 95  97 100 topcoatpeel test (Cellotape) Cross-cut 90 85  95 90  85  95 peel test (gummedtape) Gloss Δ Δ Δ Δ Δ Δ retention after weather resistance testCross-cut 95 90  98 90  90  95 peel after weather resistance test TafmerWithout Cross-cut 100  100  100 100  100 100 topcoat peel test WithCross-cut 97 100  100 97 100 100 topcoat peel test Milastomer WithoutCross-cut 100  100  100 100  100 100 topcoat peel test With Cross-cut100  97 100 97 100 100 topcoat peel test Peel off x x x x x x

INDUSTRIAL APPLICABILITY

The paint and primer of the present invention enable spray coatingwithout separation of the resin solution. Further, the coating filmformed from the paint and primer of the invention has no tackiness onthe coating film surface and exhibits excellent adhesiveness tonon-treated polyolefinic resin films, sheets or molded products.

Further, the solvent dispersion of a composite resin of the inventionhas an effect of excellent heat sealability at low temperatures, whichis conventionally not known in the art.

Also, curing agents such as a curing agent having an isocyanate group inthe molecule can be used.

The coating film obtained in the invention exhibits superior weatherresistance as compared with chlorination-modified polyolefinic coatingfilms.

Furthermore, the invention can be also used as adhesive, additive,binder, film, and primer for strippable paints and traffic paints.

Therefore, the invention is industrially useful.

What we claim is:
 1. A solvent dispersion of a composite resin, whichcomprises a solvent and a composite resin comprising a thermoplasticelastomer (A) and a polymer of copolymerizable monomers (B) consistingof a monomer having an α,β-monoethylenically unsaturated group and othercopolymerizable monomer(s), wherein the thermoplastic elastomer (A) is apropylene-based elastomer having a molecular weight distribution (Mw/Mn)of 3 or less as measured by gel permeation chromatography (GPC), and thecopolymerizable monomers (B) include at least one monomer containing nofunctional groups.
 2. The solvent dispersion of a composite resinaccording to claim 1, wherein the solvent is an organic solvent and/orwater.
 3. The solvent dispersion of a composite resin according to claim1, wherein the solvent is water and contains basic substance(s).
 4. Thesolvent dispersion of a composite resin according to claim 1, whereinthe solvent is water and contains surfactant(s).
 5. The solventdispersion of a composite resin according to claim 1, which is obtainedby removing an organic solvent from a solvent dispersion of a compositeresin comprising the organic solvent and water as the solvent, and whichcontains basic substance(s) or surfactant(s).
 6. The solvent dispersionof a composite resin according to any one of claims 3 to 5, whichcomprises water as the solvent, wherein the thermoplastic elastomer (A)and the copolymerizable monomers (B) are present in the same particle.7. The solvent dispersion of a composite resin according to claim 1,wherein the thermoplastic elastomer (A) has an intrinsic viscosity [η]of 0.1 to 12 dl/g as measured at 135° C. in decalin, and is apropylene-based elastomer (I) which contains (a) 50 to 93 mol % of aunit derived from propylene, (b) 5 to 50 mol % of a unit derived fromα-olefin, and (c) 2 to 40 mol % of a unit derived from ethylene, or apropylene-based elastomer (II) which contains (a) 50 to 95 mol % of aunit derived from propylene and (b) 5 to 50 mol % of a unit derived fromα-olefin.
 8. The solvent dispersion of a composite resin according toclaim 1, which is formed by (1) polymerizing the thermoplastic elastomer(A) and the copolymerizable monomers (B) in an organic solvent, (2)polymerizing the thermoplastic elastomer (A) and the copolymerizablemonomers (B) and then reacting the resulting polymer under radicalgeneration in an organic solvent, or (3) reacting the thermoplasticelastomer (A) and a polymer (C) composed of the copolymerizable monomers(B) under radical generation in an organic solvent.
 9. The solventdispersion of a composite resin according to claim 1, wherein the weightratio of the thermoplastic elastomer (A) and the copolymerizablemonomers (B) is such that (A)/(B)=10/90 to 90/10.
 10. The solventdispersion of a composite resin according to claim 1, wherein thethermoplastic elastomer (A) used is at least partly modified with afunctional group.
 11. A coating material containing the solventdispersion of a composite resin according to claim
 1. 12. A primercontaining the solvent dispersion of a composite resin according toclaim
 1. 13. An adhesive containing the solvent dispersion of acomposite resin according to claim
 1. 14. An additive containing thesolvent dispersion of a composite resin according to claim
 1. 15. Abinder containing the solvent dispersion of a composite resin accordingto claim
 1. 16. A film which is obtained from the solvent dispersion ofa composite resin according to claim
 1. 17. A coating material whichcontains a main agent comprising the solvent dispersion of a compositeresin according to claim 1 having active hydrogen and/or a hydroxylgroup, and a curing agent capable of reacting with the active hydrogenand/or the hydroxyl group.
 18. A primer which contains a main agentcomprising the solvent dispersion of a composite resin according toclaim 1 having active hydrogen and/or a hydroxyl group, and a curingagent capable of reacting with the active hydrogen and/or the hydroxylgroup.
 19. An adhesive which contains a main agent comprising thesolvent dispersion of a composite resin according to claim f havingactive hydrogen and/or a hydroxyl group, and a curing agent capable ofreacting with the active hydrogen and/or the hydroxyl group.
 20. Anadditive which contains a main agent comprising the solvent dispersionof a composite resin according to claim 1 having active hydrogen and/ora hydroxyl group, and a curing agent capable of reacting with the activehydrogen and/or the hydroxyl group.
 21. A binder which contains a mainagent comprising the solvent dispersion of a composite resin accordingto claim 1 having active hydrogen and/or a hydroxyl group, and a curingagent capable of reacting with the active hydrogen and/or the hydroxylgroup.
 22. A film which is formed by reacting a main agent comprisingthe solvent dispersion of a composite resin according to claim 1 havingactive hydrogen and/or a hydroxyl group with a curing agent capable ofreacting with the active hydrogen and/or the hydroxyl group.
 23. Acoating film which is formed by applying the binder according to claim15.
 24. The solvent dispersion of a composite resin according to claim4, which comprises water as the solvent, wherein the thermoplasticelastomer (A) and the copolymerizable monomers (B) are present in thesame particle.
 25. The solvent dispersion of a composite resin accordingto claim 3, which comprises water as the solvent, wherein thethermoplastic elastomer (A) and the copolymerizable monomers (B) arepresent in the same particle.
 26. A coating film which is formed byapplying the additive according to claim
 14. 27. A coating film which isformed by applying the adhesive according to claim
 13. 28. A coatingfilm which is formed by applying the primer according to claim
 12. 29. Acoating film which is formed by applying the coating material accordingto claim
 11. 30. A coating film which is formed by curing the binderaccording to claim
 21. 31. A coating film which is formed by curing theadditive according to claim
 20. 32. A coating film which is formed bycuring the adhesive according to claim
 19. 33. A coating film which isformed by curing the primer according to claim
 18. 34. A coating filmwhich is formed by curing the coating material according to claim 17.